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Sample records for supercooled molecular liquids

  1. The molecular dynamics simulation of structure and transport properties of sheared super-cooled liquid metal

    International Nuclear Information System (INIS)

    Wang Li; Liu Xiangfa; Zhang Yanning; Yang Hua; Chen Ying; Bian Xiufang

    2003-01-01

    Much more attention has been paid to the microstructure of liquid metal under non-ordinary condition recently. In this Letter, the pair correlation function (PCF), together with internal energy of sheared super-cooled liquid Co as a function of temperature has been calculated by molecular dynamics simulation based upon the embedded atom method (EAM) and analyzed compared to that under normal condition. The finding indicates that there exist three obvious peaks of PCF for liquid Co; while as the shear stress is applied to the liquid, the first and second peaks of PCF become lower, the third peak disappeared. The concentric shell structure representing short-range order of liquid still exists, however, it is weakened by the addition of shear stress, leading to the increases of disordering degree of liquid metal. The curves of energy versus temperature suggest the higher crystalline temperature compared to that under normal condition at the same cooling rate. In addition, the viscosity of super-liquid Co is calculated by non-equilibrium molecular dynamics (NEMD)

  2. Molecular dynamics study of dynamic and structural properties of supercooled liquid and glassy iron in the rapid-cooling processes

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Qi-Long; Huang, Duo-Hui; Yang, Jun-Sheng; Wan, Min-Jie; Wang, Fan-Hou, E-mail: eatonch@gmail.com

    2014-10-01

    Molecular dynamics simulations were applied to study the dynamic and structural properties of supercooled liquid and glassy iron in the rapid-cooling processes. The mean-square displacement and the non-Gaussian parameter were used to describe the dynamic properties. The evolution of structural properties was investigated using the pair distribution functions and bond-angle distribution functions. Results for dynamic and structural relaxations indicate that the dynamic features are consistently correlated with the structure evolution, and there are three temperature regions as the temperature decreases: (1) at higher temperatures (1500 K, 1300 K, and 1100 K), the system remains in the liquid characteristics during the overall relaxation process. (2) At medial temperatures (1050 K, 900 K, and 700 K), a fast β-relaxation is followed by a much slower α-relaxation. There is a little change in the structural properties in the β-relaxation region, while major configuration rearrangements occurred in the α-relaxation range and the crystallization process was completed at the end of α-relaxation region. (3) At lower temperature (500 K), the system shows glassy characteristics during the overall relaxation process. In addition, the melting temperature, glass transition temperature and diffusion coefficients of supercooled liquid iron are also computed.

  3. Strain Pattern in Supercooled Liquids

    Science.gov (United States)

    Illing, Bernd; Fritschi, Sebastian; Hajnal, David; Klix, Christian; Keim, Peter; Fuchs, Matthias

    2016-11-01

    Investigations of strain correlations at the glass transition reveal unexpected phenomena. The shear strain fluctuations show an Eshelby-strain pattern [˜cos (4 θ ) /r2 ], characteristic of elastic response, even in liquids, at long times. We address this using a mode-coupling theory for the strain fluctuations in supercooled liquids and data from both video microscopy of a two-dimensional colloidal glass former and simulations of Brownian hard disks. We show that the long-ranged and long-lived strain signatures follow a scaling law valid close to the glass transition. For large enough viscosities, the Eshelby-strain pattern is visible even on time scales longer than the structural relaxation time τ and after the shear modulus has relaxed to zero.

  4. Molecular dynamics studies of the dynamics of supercooled Lennard-Jones liquids

    International Nuclear Information System (INIS)

    De Leeuw, S.W.; Brakkee, M.J.D.

    1990-01-01

    Results are presented of molecular dynamics experiments, in which the Lennard-Jones liquid is cooled isobarically into the metastable temperature region below the freezing temperature. The variation of the density-density and transverse current correlation functions with temperature is studied. We observed a power-law behaviour for the temperature dependence of dynamical properties (viscosity and coefficienty of self-diffusion) with an exponent in good agreement with prediction of mode coupling theories and recent experimental results. (author). 23 refs, 5 figs

  5. Thermodynamic scaling of molecular dynamics in supercooled liquid state of pharmaceuticals: Itraconazole and ketoconazole.

    Science.gov (United States)

    Tarnacka, M; Madejczyk, O; Adrjanowicz, K; Pionteck, J; Kaminska, E; Kamiński, K; Paluch, M

    2015-06-14

    Pressure-Volume-Temperature (PVT) measurements and broadband dielectric spectroscopy were carried out to investigate molecular dynamics and to test the validity of thermodynamic scaling of two homologous compounds of pharmaceutical activity: itraconazole and ketoconazole in the wide range of thermodynamic conditions. The pressure coefficients of the glass transition temperature (dT(g)/dp) for itraconazole and ketoconazole were determined to be equal to 183 and 228 K/GPa, respectively. However, for itraconazole, the additional transition to the nematic phase was observed and characterized by the pressure coefficient dT(n)/dp = 258 K/GPa. From PVT and dielectric data, we obtained that the liquid-nematic phase transition is governed by the relaxation time since it occurred at constant τ(α) = 10(-5) s. Furthermore, we plotted the obtained relaxation times as a function of T(-1)v(-γ), which has revealed that the validity of thermodynamic scaling with the γ exponent equals to 3.69 ± 0.04 and 3.64 ± 0.03 for itraconazole and ketoconazole, respectively. Further analysis of the scaling parameter in itraconazole revealed that it unexpectedly decreases with increasing relaxation time, which resulted in dramatic change of the shape of the thermodynamic scaling master curve. While in the case of ketoconazole, it remained the same within entire range of data (within experimental uncertainty). We suppose that in case of itraconazole, this peculiar behavior is related to the liquid crystals' properties of itraconazole molecule.

  6. Thermodynamic scaling of molecular dynamics in supercooled liquid state of pharmaceuticals: Itraconazole and ketoconazole

    Energy Technology Data Exchange (ETDEWEB)

    Tarnacka, M., E-mail: mtarnacka@us.edu.pl; Madejczyk, O.; Kamiński, K.; Paluch, M. [Institute of Physics, University of Silesia, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Silesian Center of Education and Interdisciplinary Research, University of Silesia, ul. 75 Pulku Piechoty 1A, 41-500 Chorzow (Poland); Adrjanowicz, K. [NanoBioMedical Centre, ul. Umultowska 85, 61-614 Poznan (Poland); Pionteck, J. [Leibniz Institute of Polymer Research Dresden, Hohe Strasse 6, D-01069 Dresden (Germany); Kaminska, E. [Department of Pharmacognosy and Phytochemistry, School of Pharmacy and Division of Laboratory Medicine in Sosnowiec, Medical University of Silesia, ul. Jagiellonska 4, 41-200 Sosnowiec (Poland)

    2015-06-14

    Pressure-Volume-Temperature (PVT) measurements and broadband dielectric spectroscopy were carried out to investigate molecular dynamics and to test the validity of thermodynamic scaling of two homologous compounds of pharmaceutical activity: itraconazole and ketoconazole in the wide range of thermodynamic conditions. The pressure coefficients of the glass transition temperature (dT{sub g}/dp) for itraconazole and ketoconazole were determined to be equal to 183 and 228 K/GPa, respectively. However, for itraconazole, the additional transition to the nematic phase was observed and characterized by the pressure coefficient dT{sub n}/dp = 258 K/GPa. From PVT and dielectric data, we obtained that the liquid-nematic phase transition is governed by the relaxation time since it occurred at constant τ {sub α} = 10{sup −5} s. Furthermore, we plotted the obtained relaxation times as a function of T{sup −1}v{sup −γ}, which has revealed that the validity of thermodynamic scaling with the γ exponent equals to 3.69 ± 0.04 and 3.64 ± 0.03 for itraconazole and ketoconazole, respectively. Further analysis of the scaling parameter in itraconazole revealed that it unexpectedly decreases with increasing relaxation time, which resulted in dramatic change of the shape of the thermodynamic scaling master curve. While in the case of ketoconazole, it remained the same within entire range of data (within experimental uncertainty). We suppose that in case of itraconazole, this peculiar behavior is related to the liquid crystals’ properties of itraconazole molecule.

  7. Structure, thermodynamics, and dynamical properties of supercooled liquids

    International Nuclear Information System (INIS)

    Kambayashi, Shaw

    1992-12-01

    The equilibrium properties of supercooled liquids with repulsive soft-sphere potentials, u(r) = ε(σ/r) n , have been obtained by solving the integral equation of the theory of liquids and by performing constant-temperature molecular dynamics (MD) simulations. A thermodynamically consistent approximation, proposed recently by Rogers and Young (RY), has been examined for the supercooled soft-sphere fluids. Then, a new approximation for the integral equation, called MHNCS (modified hypernetted-chain integral equation for highly supercooled soft-sphere fluids) approximation, is proposed. The solution of the MHNCS integral equation for highly supercooled liquid states agrees well with the results of computer simulations. The MHNCS integral equation has also been applied for binary soft-sphere mixtures. Dynamical properties of soft-sphere fluids have been investigated by molecular dynamics (MD) simulations. The reduced diffusion constant is found to be insensitive to the choice of the softness of the potential. On the other hand, the spectrum of the velocity autocorrelation function shows a pronounced dependence on the softness of the potential. These significant dynamical properties dependent on the softness parameter (n) are consistent to dynamical behavior observed in liquid alkali metals and liquefied inert gases. The self-part of the density-density autocorrelation function obtained shows a clear nonexponential decay in intermediate time, as the liquid-glass transition is approached. (J.P.N.) 105 refs

  8. Molecular dynamics in supercooled liquid and glassy states of antibiotics: azithromycin, clarithromycin and roxithromycin studied by dielectric spectroscopy. Advantages given by the amorphous state.

    Science.gov (United States)

    Adrjanowicz, K; Zakowiecki, D; Kaminski, K; Hawelek, L; Grzybowska, K; Tarnacka, M; Paluch, M; Cal, K

    2012-06-04

    Antibiotics are chemical compounds of extremely important medical role. Their history can be traced back more than one hundred years. Despite the passing time and significant progress made in pharmacy and medicine, treatment of many bacterial infections without antibiotics would be completely impossible. This makes them particularly unique substances and explains the unflagging popularity of antibiotics within the medical community. Herein, using dielectric spectroscopy we have studied the molecular mobility in the supercooled liquid and glassy states of three well-known antibiotic agents: azithromycin, clarithromycin and roxithromycin. Dielectric studies revealed a number of relaxation processes of different molecular origin. Besides the primary α-relaxation, observed above the respective glass transition temperatures of antibiotics, two secondary relaxations in the glassy state were identified. Interestingly, the fragility index as well as activation energies of the secondary processes turned out to be practically the same for all three compounds, indicating probably much the same molecular dynamics. Long-term stability of amorphous antibiotics at room temperature was confirmed by X-ray diffraction technique, and calorimetric studies were performed to evaluate the basic thermodynamic parameters. Finally, we have also checked the experimental solubility advantages given by the amorphous form of the examined antibiotics.

  9. Evidence for compact cooperatively rearranging regions in a supercooled liquid

    International Nuclear Information System (INIS)

    Elenius, M; Dzugutov, M

    2009-01-01

    We examine structural relaxation in a supercooled glass-forming liquid simulated by constant-energy constant-volume (NVE) molecular dynamics. Time correlations of the total kinetic energy fluctuations are used as a comprehensive measure of the system's approach to the ergodic equilibrium. We find that, under cooling, the total structural relaxation becomes delayed as compared with the decay of the component of the intermediate scattering function corresponding to the main peak of the structure factor. This observation can be explained by collective movements of particles preserving many-body structural correlations within compact three-dimensional (3D) cooperatively rearranging regions.

  10. Prediction of supercooled liquid vapor pressures and n-octanol/air partition coefficients for polybrominated diphenyl ethers by means of molecular descriptors from DFT method

    International Nuclear Information System (INIS)

    Wang Zunyao; Zeng Xiaolan; Zhai Zhicai

    2008-01-01

    The molecular geometries of 209 polybrominated diphenyl ethers (PBDEs) were optimized at the B3LYP/6-31G* level with Gaussian 98 program. The calculated structural parameters were taken as theoretical descriptors to establish two novel QSPR models for predicting supercooled liquid vapor pressures (P L ) and octanol/air partition coefficients (K OA ) of PBDEs based on the theoretical linear solvation energy relationship (TLSER) model, respectively. The two models achieved in this work both contain three variables: most negative atomic partial charge in molecule (q - ), dipole moment of the molecules (μ) and mean molecular polarizability (α), of which R 2 values are both as high as 0.997, their root-mean-square errors in modeling (RSMEE) are 0.069 and 0.062 respectively. In addition, the F-value of two models are both evidently larger than critical values F 0.05 and the variation inflation factors (VIF) of variables herein are all less than 5.0, suggesting obvious statistic significance of the P L and K OA predicting models. The results of Leave-One-Out (LOO) cross-validation for training set and validation with external test set both show that the two models obtained exhibited optimum stability and good predictive power. We suggest that the QSPRs derived here can be used to predict accurately P L and K OA for non-tested PBDE congeners from Mono-BDEs to Hepta-BDEs and from Mono-BDEs to Hexa-BDEs, respectively

  11. Polarized View of Supercooled Liquid Water Clouds

    Science.gov (United States)

    Alexandrov, Mikhail D.; Cairns, Brian; Van Diedenhoven, Bastiaan; Ackerman, Andrew S.; Wasilewski, Andrzej P.; McGill, Matthew J.; Yorks, John E.; Hlavka, Dennis L.; Platnick, Steven E.; Arnold, G. Thomas

    2016-01-01

    Supercooled liquid water (SLW) clouds, where liquid droplets exist at temperatures below 0 C present a well known aviation hazard through aircraft icing, in which SLW accretes on the airframe. SLW clouds are common over the Southern Ocean, and climate-induced changes in their occurrence is thought to constitute a strong cloud feedback on global climate. The two recent NASA field campaigns POlarimeter Definition EXperiment (PODEX, based in Palmdale, California, January-February 2013) and Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS, based in Houston, Texas in August- September 2013) provided a unique opportunity to observe SLW clouds from the high-altitude airborne platform of NASA's ER-2 aircraft. We present an analysis of measurements made by the Research Scanning Polarimeter (RSP) during these experiments accompanied by correlative retrievals from other sensors. The RSP measures both polarized and total reflectance in 9 spectral channels with wavelengths ranging from 410 to 2250 nm. It is a scanning sensor taking samples at 0.8deg intervals within 60deg from nadir in both forward and backward directions. This unique angular resolution allows for characterization of liquid water droplet size using the rainbow structure observed in the polarized reflectances in the scattering angle range between 135deg and 165deg. Simple parametric fitting algorithms applied to the polarized reflectance provide retrievals of the droplet effective radius and variance assuming a prescribed size distribution shape (gamma distribution). In addition to this, we use a non-parametric method, Rainbow Fourier Transform (RFT),which allows retrieval of the droplet size distribution without assuming a size distribution shape. We present an overview of the RSP campaign datasets available from the NASA GISS website, as well as two detailed examples of the retrievals. In these case studies we focus on cloud fields with spatial features

  12. Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition.

    Science.gov (United States)

    Smith, R Scott; Kay, Bruce D

    2012-03-15

    Experimental measurements of the properties of supercooled liquids at temperatures near their glass transition temperatures, Tg, are requisite for understanding the behavior of glasses and amorphous solids. Unfortunately, many supercooled molecular liquids rapidly crystallize at temperatures far above their Tg, making such measurements difficult to nearly impossible. In this Perspective, we discuss some recent alternative approaches to obtain experimental data in the temperature regime near Tg. These new approaches may yield the additional experimental data necessary to test current theoretical models of the dynamical slowdown that occurs in supercooled liquids approaching the glass transition.

  13. Microscopic Theory for the Role of Attractive Forces in the Dynamics of Supercooled Liquids.

    Science.gov (United States)

    Dell, Zachary E; Schweizer, Kenneth S

    2015-11-13

    We formulate a microscopic, no adjustable parameter, theory of activated relaxation in supercooled liquids directly in terms of the repulsive and attractive forces within the framework of pair correlations. Under isochoric conditions, attractive forces can nonperturbatively modify slow dynamics, but at high enough density their influence vanishes. Under isobaric conditions, attractive forces play a minor role. High temperature apparent Arrhenius behavior and density-temperature scaling are predicted. Our results are consistent with recent isochoric simulations and isobaric experiments on a deeply supercooled molecular liquid. The approach can be generalized to treat colloidal gelation and glass melting, and other soft matter slow dynamics problems.

  14. Supercooled liquid dynamics for the charged hard-sphere model

    International Nuclear Information System (INIS)

    Lai, S.K.; Chang, S.Y.

    1994-08-01

    We study the dynamics of supercooled liquid and the liquid-glass transition by applying the mode coupling theory to the charged hard-sphere model. By exploiting the two independent parameters inherent in the charged hard-sphere system we examine structurally the subtle and competitive role played by the short-range hard-core correlation and the long-range Coulomb tail. It is found in this work that the long-range Coulombic charge factor effect is generally a less effective contribution to structure when the plasma parameter is less than 500 and becomes dominant when it is greater thereof. To extend our understanding of the supercooled liquid and the liquid-glass transition, an attempt is made to calculate and to give physical relevance to the mode-coupling parameters which are frequently used as mere fitting parameters in analysis of experiments on supercooled liquid systems. This latter information enables us to discuss the possible application of the model to a realistic system. (author). 22 refs, 4 figs

  15. Liquid phase and supercooled liquid phase welding of bulk metallic glasses

    International Nuclear Information System (INIS)

    Kawamura, Y.

    2004-01-01

    Recent progress on welding in bulk metallic glasses (BMGs) has been reviewed. BMGs have been successfully welded to BMGs or crystalline metals by liquid phase welding using explosion, pulse-current and electron-beam methods, and by supercooled liquid phase welding using friction method. Successful welding of the liquid phase methods was due to the high glass-forming ability of the BMGs and the high concentration of welding energy in these methods. In contrast, the supercooled liquid phase welding was successful due to the thermally stable supercooled liquid state of the BMGs and the superplasticity and viscous flow of the supercooled liquid. The successful welding of BMGs to BMGs and crystalline materials is promising for the future development of BMGs as engineering materials

  16. Mixing effects in the crystallization of supercooled quantum binary liquids

    International Nuclear Information System (INIS)

    Kühnel, M.; Kalinin, A.; Fernández, J. M.; Tejeda, G.; Moreno, E.; Montero, S.; Tramonto, F.; Galli, D. E.; Nava, M.; Grisenti, R. E.

    2015-01-01

    By means of Raman spectroscopy of liquid microjets, we have investigated the crystallization process of supercooled quantum liquid mixtures composed of parahydrogen (pH 2 ) or orthodeuterium (oD 2 ) diluted with small amounts of neon. We show that the introduction of the Ne impurities affects the crystallization kinetics in terms of a significant reduction of the measured pH 2 and oD 2 crystal growth rates, similarly to what found in our previous work on supercooled pH 2 -oD 2 liquid mixtures [Kühnel et al., Phys. Rev. B 89, 180201(R) (2014)]. Our experimental results, in combination with path-integral simulations of the supercooled liquid mixtures, suggest in particular a correlation between the measured growth rates and the ratio of the effective particle sizes originating from quantum delocalization effects. We further show that the crystalline structure of the mixtures is also affected to a large extent by the presence of the Ne impurities, which likely initiate the freezing process through the formation of Ne-rich crystallites

  17. Mixing effects in the crystallization of supercooled quantum binary liquids

    Energy Technology Data Exchange (ETDEWEB)

    Kühnel, M.; Kalinin, A. [Institut für Kernphysik, J. W. Goethe-Universität, Max-von-Laue-Str. 1, 60438 Frankfurt am Main (Germany); Fernández, J. M.; Tejeda, G.; Moreno, E.; Montero, S. [Laboratory of Molecular Fluid Dynamics, Instituto de Estructura de la Materia, CSIC, Serrano 121, 28006 Madrid (Spain); Tramonto, F.; Galli, D. E. [Laboratorio di Calcolo Parallelo e di Simulazioni di Materia Condensata, Dipartimento di Fisica, Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Nava, M. [Laboratorio di Calcolo Parallelo e di Simulazioni di Materia Condensata, Dipartimento di Fisica, Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Computational Science, Department of Chemistry and Applied Biosciences, ETH Zurich, USI Campus, Via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Grisenti, R. E. [Institut für Kernphysik, J. W. Goethe-Universität, Max-von-Laue-Str. 1, 60438 Frankfurt am Main (Germany); GSI - Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, 64291 Darmstadt (Germany)

    2015-08-14

    By means of Raman spectroscopy of liquid microjets, we have investigated the crystallization process of supercooled quantum liquid mixtures composed of parahydrogen (pH{sub 2}) or orthodeuterium (oD{sub 2}) diluted with small amounts of neon. We show that the introduction of the Ne impurities affects the crystallization kinetics in terms of a significant reduction of the measured pH{sub 2} and oD{sub 2} crystal growth rates, similarly to what found in our previous work on supercooled pH{sub 2}-oD{sub 2} liquid mixtures [Kühnel et al., Phys. Rev. B 89, 180201(R) (2014)]. Our experimental results, in combination with path-integral simulations of the supercooled liquid mixtures, suggest in particular a correlation between the measured growth rates and the ratio of the effective particle sizes originating from quantum delocalization effects. We further show that the crystalline structure of the mixtures is also affected to a large extent by the presence of the Ne impurities, which likely initiate the freezing process through the formation of Ne-rich crystallites.

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

    Science.gov (United States)

    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.

  19. Structural crossover in a supercooled metallic liquid and the link to a liquid-to-liquid phase transition

    Energy Technology Data Exchange (ETDEWEB)

    Lan, S.; Ma, J. L.; Fan, J. [Department of Physics and Material Science, City University of Hong Kong 83 Tat Chee Ave., Kowloon (Hong Kong); Blodgett, M.; Kelton, K. F. [Department of Physics and Institute of Materials Science and Engineering, Washington University One Brookings Drive, St. Louis, Missouri 63130-4899 (United States); Wang, X.-L., E-mail: xlwang@cityu.edu.hk [Department of Physics and Material Science, City University of Hong Kong 83 Tat Chee Ave., Kowloon (Hong Kong); City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057 (China)

    2016-05-23

    Time-resolved synchrotron measurements were carried out to capture the structure evolution of an electrostatically levitated metallic-glass-forming liquid during free cooling. The experimental data shows a crossover in the liquid structure at ∼1000 K, about 115 K below the melting temperature and 150 K above the crystallization temperature. The structure change is characterized by a dramatic growth in the extended-range order below the crossover temperature. Molecular dynamics simulations have identified that the growth of the extended-range order was due to an increased correlation between solute atoms. These results provide structural evidence for a liquid-to-liquid-phase-transition in the supercooled metallic liquid.

  20. Tensorial analysis of Eshelby stresses in 3D supercooled liquids

    Science.gov (United States)

    Lemaître, Anaël

    2015-10-01

    It was recently proposed that the local rearrangements governing relaxation in supercooled liquids impress on the liquid medium long-ranged (Eshelby) stress fluctuations that accumulate over time. From this viewpoint, events must be characterized by elastic dipoles, which are second order tensors, and Eshelby fields are expected to show up in stress and stress increment correlations, which are fourth order tensor fields. We construct here an analytical framework that permits analyzing such tensorial correlations in isotropic media in view of accessing Eshelby fields. Two spherical bases are introduced, which correspond to Cartesian and spherical coordinates for tensors. We show how they can be used to decompose stress correlations and thus test such properties as isotropy and power-law scalings. Eshelby fields and the predicted stress correlations in an infinite medium are shown to belong to an algebra that can conveniently be described using the spherical tensor bases. Using this formalism, we demonstrate that the inherent stress field of 3D supercooled liquids is power law correlated and carries the signature of Eshelby fields, thus supporting the idea that relaxation events give rise to Eshelby stresses that accumulate over time.

  1. Linking density functional and mode coupling models for supercooled liquids

    Energy Technology Data Exchange (ETDEWEB)

    Premkumar, Leishangthem; Bidhoodi, Neeta; Das, Shankar P. [School of Physical Sciences, Jawaharlal Nehru University, New Delhi 110067 (India)

    2016-03-28

    We compare predictions from two familiar models of the metastable supercooled liquid, respectively, constructed with thermodynamic and dynamic approaches. In the so called density functional theory the free energy F[ρ] of the liquid is a functional of the inhomogeneous density ρ(r). The metastable state is identified as a local minimum of F[ρ]. The sharp density profile characterizing ρ(r) is identified as a single particle oscillator, whose frequency is obtained from the parameters of the optimum density function. On the other hand, a dynamic approach to supercooled liquids is taken in the mode coupling theory (MCT) which predict a sharp ergodicity-non-ergodicity transition at a critical density. The single particle dynamics in the non-ergodic state, treated approximately, represents a propagating mode whose characteristic frequency is computed from the corresponding memory function of the MCT. The mass localization parameters in the above two models (treated in their simplest forms) are obtained, respectively, in terms of the corresponding natural frequencies depicted and are shown to have comparable magnitudes.

  2. Linking density functional and mode coupling models for supercooled liquids.

    Science.gov (United States)

    Premkumar, Leishangthem; Bidhoodi, Neeta; Das, Shankar P

    2016-03-28

    We compare predictions from two familiar models of the metastable supercooled liquid, respectively, constructed with thermodynamic and dynamic approaches. In the so called density functional theory the free energy F[ρ] of the liquid is a functional of the inhomogeneous density ρ(r). The metastable state is identified as a local minimum of F[ρ]. The sharp density profile characterizing ρ(r) is identified as a single particle oscillator, whose frequency is obtained from the parameters of the optimum density function. On the other hand, a dynamic approach to supercooled liquids is taken in the mode coupling theory (MCT) which predict a sharp ergodicity-non-ergodicity transition at a critical density. The single particle dynamics in the non-ergodic state, treated approximately, represents a propagating mode whose characteristic frequency is computed from the corresponding memory function of the MCT. The mass localization parameters in the above two models (treated in their simplest forms) are obtained, respectively, in terms of the corresponding natural frequencies depicted and are shown to have comparable magnitudes.

  3. Breaking through the glass ceiling: The correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films

    Science.gov (United States)

    Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

    2010-03-01

    Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, Tg (103 K). Layered films, consisting of CH3OH and CD3OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above Tg. The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.

  4. Mechanical annealing in the flow of supercooled metallic liquid

    International Nuclear Information System (INIS)

    Zhang, Meng; Dai, Lan Hong; Liu, Lin

    2014-01-01

    Flow induced structural evolution in a supercooled metallic liquid Vit106a (Zr 58.5 Cu 15.6 Al 10.3 Ni 12.8 Nb 2.8 , at. %) was investigated via uni-axial compression combined with differential scanning calorimeter (DSC). Compression tests at strain rates covering the transition from Newtonian flow to non-Newtonian flow and at the same strain rate 2 × 10 −1 s −1 to different strains were performed at the end of glass transition (T g-end  = 703 K). The relaxation enthalpies measured by DSC indicate that the samples underwent non-Newtonian flow contain more free volume than the thermally annealed sample (703 K, 4 min), while the samples underwent Newtonian flow contain less, namely, the free volume of supercooled metallic liquids increases in non-Newtonian flow, while decreases in Newtonian flow. The oscillated variation of the relaxation enthalpies of the samples deformed at the same strain rate 2 × 10 −1 s −1 to different strains confirms that the decrease of free volume was caused by flow stress, i.e., “mechanical annealing.” Micro-hardness tests were also performed to show a similar structural evolution tendency. Based on the obtained results, the stress-temperature scaling in the glass transition of metallic glasses are supported experimentally, as stress plays a role similar to temperature in the creation and annihilation of free volume. In addition, a widening perspective angle on the glass transition of metallic glasses by exploring the 3-dimensional stress-temperature-enthalpy phase diagram is presented. The implications of the observed mechanical annealing effect on the amorphous structure and the work-hardening mechanism of metallic glasses are elucidated based on atomic level stress model

  5. Liquid structure and temperature invariance of sound velocity in supercooled Bi melt

    International Nuclear Information System (INIS)

    Emuna, M.; Mayo, M.; Makov, G.; Greenberg, Y.; Caspi, E. N.; Yahel, E.; Beuneu, B.

    2014-01-01

    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 structural 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

  6. Behavior of supercooled aqueous solutions stemming from hidden liquid-liquid transition in water.

    Science.gov (United States)

    Biddle, John W; Holten, Vincent; Anisimov, Mikhail A

    2014-08-21

    A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid-liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid-liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H2O-NaCl and H2O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid-liquid transition. We elucidate the non-conserved nature of the order parameter (extent of "reaction" between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

  7. Local structure and structural signature underlying properties in metallic glasses and supercooled liquids

    Science.gov (United States)

    Ding, Jun

    Metallic glasses (MGs), discovered five decades ago as a newcomer in the family of glasses, are of current interest because of their unique structures and properties. There are also many fundamental materials science issues that remain unresolved for metallic glasses, as well as their predecessor above glass transition temperature, the supercooled liquids. In particular, it is a major challenge to characterize the local structure and unveil the structure-property relationship for these amorphous materials. This thesis presents a systematic study of the local structure of metallic glasses as well as supercooled liquids via classical and ab initio molecular dynamics simulations. Three typical MG models are chosen as representative candidate, Cu64 Zr36, Pd82Si18 and Mg65Cu 25Y10 systems, while the former is dominant with full icosahedra short-range order and the prism-type short-range order dominate for latter two. Furthermore, we move to unravel the underlying structural signature among several properties in metallic glasses. Firstly, the temperature dependence of specific heat and liquid fragility between Cu-Zr and Mg-Cu-Y (also Pd-Si) in supercooled liquids are quite distinct: gradual versus fast evolution of specific heat and viscosity/relaxation time with undercooling. Their local structural ordering are found to relate with the temperature dependence of specific heat and relaxation time. Then elastic heterogeneity has been studied to correlate with local structure in Cu-Zr MGs. Specifically, this part covers how the degree of elastic deformation correlates with the internal structure at the atomic level, how to quantitatively evaluate the local solidity/liquidity in MGs and how the network of interpenetrating connection of icosahedra determine the corresponding shear modulus. Finally, we have illustrated the structure signature of quasi-localized low-frequency vibrational normal modes, which resides the intriguing vibrational properties in MGs. Specifically, the

  8. Kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation

    International Nuclear Information System (INIS)

    Zhou Lili; Liu Rangsu; Tian Zean; Liu Hairong; Hou Zhaoyang; Peng Ping; Zhu Xuanmin; Liu Quanhui

    2012-01-01

    The kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation process have been investigated by molecular dynamics simulations, and the microstructure evolution analyzed by the cluster-type index method (CTIM) and the tracing method. It has been found that, the dynamic features are consistently correlated with the microstructure evolution and the crystallization characteristics in the mean square displacement (MSD) and the non-Gaussian parameter (NGP): the β relaxation regime corresponds to the minor structural rearrangement because of the “cage effect”, and the atoms attempt to escape from the “cages”; the α relaxation regime is related to a more diffusive movement of atoms, and the appearance of the second plateau in MSD and the non-zero plateau in NGP corresponds to the completion of crystallization. In addition, three distinct stages of nucleation, growth of nuclei and coarsening of crystallites in the crystallization process have been clearly revealed.

  9. Correlation between local structure and stability of supercooled liquid state in Zr-based metallic glasses

    International Nuclear Information System (INIS)

    Saida, Junji; Imafuku, Muneyuki; Sato, Shigeo; Sanada, Takashi; Matsubara, Eiichiro; Inoue, Akihisa

    2007-01-01

    The correlation between the local structure and stability of supercooled liquid state is investigated in the Zr 70 (Ni, Cu) 30 binary and Zr 70 Al 10 (Ni, Cu) 20 (numbers indicate at.%) ternary metallic glasses. The Zr 70 Ni 30 binary amorphous alloy with a low stability of supercooled liquid state has a tetragonal Zr 2 Ni-like local structure around Ni atom. Meanwhile, the Zr 70 Cu 30 binary metallic glass has a different local structure of tetragonal Zr 2 Cu, where we suggest the icosahedral local structure by the quasicrystallization behavior in addition of a very small amount of noble metals. The effect of Al addition on the local structure in the Zr-Ni alloy is also examined. We have investigated that the dominant local structure changes in the icosahedral-like structure from the tetragonal Zr 2 Ni-like local structure by the Al substitution with Ni accompanying with the significant stabilization of supercooled liquid state. It is concluded that the formation of icosahedral local structure contributes to the enhancement of stability of supercooled liquid state in the Zr-based alloys

  10. The nucleation process and the roles of structure and density fluctuations in supercooled liquid Fe

    International Nuclear Information System (INIS)

    Li, Rong; Wu, Yongquan; Xiao, Junjiang

    2014-01-01

    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 clusters 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

  11. Rotational dynamics in supercooled water from nuclear spin relaxation and molecular simulations.

    Science.gov (United States)

    Qvist, Johan; Mattea, Carlos; Sunde, Erik P; Halle, Bertil

    2012-05-28

    Structural dynamics in liquid water slow down dramatically in the supercooled regime. To shed further light on the origin of this super-Arrhenius temperature dependence, we report high-precision (17)O and (2)H NMR relaxation data for H(2)O and D(2)O, respectively, down to 37 K below the equilibrium freezing point. With the aid of molecular dynamics (MD) simulations, we provide a detailed analysis of the rotational motions probed by the NMR experiments. The NMR-derived rotational correlation time τ(R) is the integral of a time correlation function (TCF) that, after a subpicosecond librational decay, can be described as a sum of two exponentials. Using a coarse-graining algorithm to map the MD trajectory on a continuous-time random walk (CTRW) in angular space, we show that the slowest TCF component can be attributed to large-angle molecular jumps. The mean jump angle is ∼48° at all temperatures and the waiting time distribution is non-exponential, implying dynamical heterogeneity. We have previously used an analogous CTRW model to analyze quasielastic neutron scattering data from supercooled water. Although the translational and rotational waiting times are of similar magnitude, most translational jumps are not synchronized with a rotational jump of the same molecule. The rotational waiting time has a stronger temperature dependence than the translation one, consistent with the strong increase of the experimentally derived product τ(R) D(T) at low temperatures. The present CTRW jump model is related to, but differs in essential ways from the extended jump model proposed by Laage and co-workers. Our analysis traces the super-Arrhenius temperature dependence of τ(R) to the rotational waiting time. We present arguments against interpreting this temperature dependence in terms of mode-coupling theory or in terms of mixture models of water structure.

  12. Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

    Directory of Open Access Journals (Sweden)

    Bo Jakobsen

    2016-05-01

    Full Text Available We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat conduction through an insulating material, i.e., is proportional to the temperature difference between sample and surroundings. The monitored signal reflects the sample’s specific heat and is sensitive to exo- and endothermic processes. The technique is useful for studying supercooled liquids and their crystallization, e.g., for locating the glass transition and melting point(s, as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition.

  13. Bond orientational ordering in a metastable supercooled liquid: a shadow of crystallization and liquid–liquid transition

    International Nuclear Information System (INIS)

    Tanaka, Hajime

    2010-01-01

    It is widely believed that a liquid state can be characterized by a single order parameter, density, and that a transition from a liquid to solid can be described by density ordering (translational ordering). For example, this type of theory has had great success in describing the phase behaviour of hard spheres. However, there are some features that cannot be captured by such theories. For example, hard spheres crystallize into either hcp or fcc structures, without a tendency of bcc ordering which is expected by the Alexander–McTague theory based on the Landau-type free energy of the density order parameter. We also found hcp-like bond orientational ordering in a metastable supercooled liquid, which promotes nucleation of hcp crystals. Furthermore, theories based on the single order parameter cannot explain water-like thermodynamic and kinetic anomalies of a liquid and liquid–liquid transition in a single-component liquid. Based on these facts, we argue that we need an additional order parameter to describe a liquid state. It is bond orientational order, which is induced by dense packing in hard spheres or by directional bonding in molecular and atomic liquids. Bond orientational order is intrinsically of local nature, unlike translational order which is of global nature. This feature plays a unique role in crystallization and quasicrystal formation. We also reveal that bond orientational ordering is a cause of dynamic heterogeneity near a glass transition and is linked to slow dynamics. In relation to this, we note that, for describing the structuring of a highly disordered liquid, we need a structural signature of low configurational entropy, which is more general than bond orientational order. Finally, the water-like anomaly and liquid–liquid transition can be explained by bond orientational ordering due to hydrogen or covalent bonding and its cooperativity, respectively. So we argue that bond orientational ordering is a key to the physical understanding

  14. Heterogeneous nucleation from a supercooled ionic liquid on a carbon surface.

    Science.gov (United States)

    He, Xiaoxia; Shen, Yan; Hung, Francisco R; Santiso, Erik E

    2016-12-07

    Classical molecular dynamics simulations were used to study the nucleation of the crystal phase of the ionic liquid [dmim + ][Cl - ] from its supercooled liquid phase, both in the bulk and in contact with a graphitic surface of D = 3 nm. By combining the string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)], with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [Santiso and Trout, J. Chem. Phys. 134, 064109 (2011)], we computed minimum free energy paths, the approximate size of the critical nucleus, the free energy barrier, and the rates involved in these nucleation processes. For homogeneous nucleation, the subcooled liquid phase has to overcome a free energy barrier of ∼85 kcal/mol to form a critical nucleus of size ∼3.6 nm, which then grows into the monoclinic crystal phase. This free energy barrier becomes about 42% smaller (∼49 kcal/mol) when the subcooled liquid phase is in contact with a graphitic disk, and the critical nucleus formed is about 17% smaller (∼3.0 nm) than the one observed for homogeneous nucleation. The crystal formed in the heterogeneous nucleation scenario has a structure that is similar to that of the bulk crystal, with the exception of the layers of ions next to the graphene surface, which have larger local density and the cations lie with their imidazolium rings parallel to the graphitic surface. The critical nucleus forms near the graphene surface separated only by these layers of ions. The heterogeneous nucleation rate (∼4.8 × 10 11 cm -3 s -1 ) is about one order of magnitude faster than the homogeneous rate (∼6.6 × 10 10 cm -3 s -1 ). The computed free energy barriers and nucleation rates are in reasonable agreement with experimental and simulation values obtained for the homogeneous and heterogeneous nucleation of other systems (ice, urea, Lennard-Jones spheres, and oxide

  15. Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

    DEFF Research Database (Denmark)

    Jakobsen, Bo; Sanz, Alejandro; Niss, Kristine

    2016-01-01

    and their crystallization, e.g., for locating the glass transition and melting point(s), as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition......We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat...

  16. Predicting How Nanoconfinement Changes the Relaxation Time of a Supercooled Liquid

    DEFF Research Database (Denmark)

    Ingebrigtsen, Trond; Errington, Jeff; Truskett, Tom

    2013-01-01

    The properties of nanoconfined fluids can be strikingly different from those of bulk liquids. A basic unanswered question is whether the equilibrium and dynamic consequences of confinement are related to each other in a simple way. We study this question by simulation of a liquid comprising...... asymmetric dumbbell-shaped molecules, which can be deeply supercooled without crystallizing. We find that the dimensionless structural relaxation times—spanning six decades as a function of temperature, density, and degree of confinement—collapse when plotted versus excess entropy. The data also collapse...

  17. Predicting how nanoconfinement changes the relaxation time of a supercooled liquid.

    Science.gov (United States)

    Ingebrigtsen, Trond S; Errington, Jeffrey R; Truskett, Thomas M; Dyre, Jeppe C

    2013-12-06

    The properties of nanoconfined fluids can be strikingly different from those of bulk liquids. A basic unanswered question is whether the equilibrium and dynamic consequences of confinement are related to each other in a simple way. We study this question by simulation of a liquid comprising asymmetric dumbbell-shaped molecules, which can be deeply supercooled without crystallizing. We find that the dimensionless structural relaxation times-spanning six decades as a function of temperature, density, and degree of confinement-collapse when plotted versus excess entropy. The data also collapse when plotted versus excess isochoric heat capacity, a behavior consistent with the existence of isomorphs in the bulk and confined states.

  18. Density of states of colloidal glasses and supercooled liquids

    NARCIS (Netherlands)

    Ghosh, A.; Mari, R.; Chikkadi, V.; Schall, P.; Kurchan, J.; Bonn, D.

    2010-01-01

    The glass transition is perhaps the greatest unsolved problem in condensed matter physics: the main question is how to reconcile the liquid-like structure with solid-like mechanical properties. In solids, structure and mechanics are related directly through the vibrational density of states of the

  19. Applications and limitations of electron correlation microscopy to study relaxation dynamics in supercooled liquids

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Pei; He, Li [Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI 53706 (United States); Besser, Matthew F. [Materials Science and Engineering, Ames Laboratory, Iowa State University, Ames, IA 50011 (United States); Liu, Ze; Schroers, Jan [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, CT 06511 (United States); Kramer, Matthew J. [Materials Science and Engineering, Ames Laboratory, Iowa State University, Ames, IA 50011 (United States); Voyles, Paul M., E-mail: paul.voyles@wisc.edu [Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2017-07-15

    Electron correlation microscopy (ECM) is a way to measure structural relaxation times, τ, of liquids with nanometer-scale spatial resolution using coherent electron scattering equivalent of photon correlation spectroscopy. We have applied ECM with a 3.5 nm diameter probe to Pt{sub 57.5}Cu{sub 14.7}Ni{sub 5.3}P{sub 22.5} amorphous nanorods and Pd{sub 40}Ni{sub 40}P{sub 20} bulk metallic glass (BMG) heated inside the STEM into the supercooled liquid region. These data demonstrate that the ECM technique is limited by the characteristics of the time series, which must be at least 40τ to obtain a well-converged correlation function g{sub 2}(t), and the time per frame, which must be less than 0.1τ to obtain sufficient sampling. A high-speed direct electron camera enables fast acquisition and affords reliable g{sub 2}(t) data even with low signal per frame. - Highlights: • Electron Correlation Microscopy (ECM) technique was applied to measure structural relaxation times of supercooled liquids in metallic glass. • In Pt{sub 57.5}Cu{sub 14.7}Ni{sub 5.3}P{sub 22.5} nanowire, τ and β decreases over the measured supercooled liquid regime. • In Pd{sub 40}Ni{sub 40}P{sub 20} bulk alloy, τ decreases from T{sub g}+28 °C to T{sub g}+48 °C, then increases as the temperature approaches T{sub x}. • ECM experiment requires a length of time series at least 40 times the characteristic relaxation time and a time per diffraction pattern at most 0.1 times the relaxation time.

  20. Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

    Energy Technology Data Exchange (ETDEWEB)

    Biddle, John W.; Holten, Vincent; Anisimov, Mikhail A., E-mail: anisimov@umd.edu [Institute for Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

    2014-08-21

    A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid–liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid–liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H{sub 2}O-NaCl and H{sub 2}O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid–liquid transition. We elucidate the non-conserved nature of the order parameter (extent of “reaction” between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

  1. Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

    International Nuclear Information System (INIS)

    Biddle, John W.; Holten, Vincent; Anisimov, Mikhail A.

    2014-01-01

    A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid–liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid–liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H 2 O-NaCl and H 2 O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid–liquid transition. We elucidate the non-conserved nature of the order parameter (extent of “reaction” between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases

  2. Orientational ordering as a possible mechanism for viscosity-enhancement of supercooled liquids

    International Nuclear Information System (INIS)

    Dattagupta, S.

    1990-07-01

    A supercooled liquid is viewed to have regions of local orientational order which can be picturized in terms of cages that restrict single particle diffusion. The mismatch in the orientation of two locally ordered neighbouring regions causes an internal stress which is added to the stress that appears in the Maxwell model of viscoelasticity. This leads to a ''renormalized'' Maxwell time which is related to the susceptibility associated with the orientational order. Hence, when the latter becomes very large, one obtains a large enhancement of the viscosity. (author). 7 refs

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

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Rakesh S.; Debenedetti, Pablo G. [Department of Chemical & Biological Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Biddle, John W.; Anisimov, Mikhail A., E-mail: anisimov@umd.edu [Institute of Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

    2016-04-14

    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, 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.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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, 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.

  5. Using Peltier cells to study solid-liquid-vapour transitions and supercooling

    International Nuclear Information System (INIS)

    Torzo, Giacomo; Soletta, Isabella; Branca, Mario

    2007-01-01

    We propose an apparatus for teaching experimental thermodynamics in undergraduate introductory courses, using thermoelectric modules and a real-time data acquisition system. The device may be made at low cost, still providing an easy approach to the investigation of liquid-solid and liquid-vapour phase transitions and of metastable states (supercooling). The thermoelectric module (a technological evolution of the thermocouple) is by itself an interesting subject that offers a clear example of both thermo-electric (Seebeck effect) and electro-thermal (Peltier effect) energy transformation. We report here some cooling/heating measurements for several liquids and mixtures, including water, salt/water, ethanol/water and sodium acetate, showing how to evaluate the phenomena of freezing point depression and elevation, and how to evaluate the water latent heat

  6. Correlation between supercooled liquid relaxation and glass poisson’s ratio

    DEFF Research Database (Denmark)

    Sun, Q.J.; Hu, L.N.; Zhou, C.

    2015-01-01

    in the ratio r and this relation can be described by the empirical function v = 0.5 − A ∗ exp(−B ∗ r), where A and B are constants. This correlation might imply that glass plasticity is associated with the competition between the α and the slow β relaxations in SLs. The underlying physics of this correlation......We report on a correlation between the supercooled liquid (SL) relaxation and glass Poisson’s ratio (v) by comparing the activation energy ratio (r) of the α and the slow β relaxations and the v values for both metallic and nonmetallic glasses. Poisson’s ratio v generally increases with an increase...... lies in the heredity of the structural heterogeneity from liquid to glass. This work gives insights into both the microscopic mechanism of glass deformation through the SL dynamics and the complex structural evolution during liquid-glass transition....

  7. Elastic properties of Pd40Cu30Ni10P20 bulk glass in supercooled liquid region

    DEFF Research Database (Denmark)

    Nishiyama, N.; Inoue, A.; Jiang, Jianzhong

    2001-01-01

    In situ ultrasonic measurements for the Pd40Cu30Ni10P20 bulk glass in three states: Glassy solid, supercooled liquid, and crystalline, have been performed. It is found that velocities of both longitudinal and transverse waves and elastic moduli (shear modulus, bulk modulus, Young's modulus......, and Lame parameter), together with Debye temperature, gradually decrease with increasing temperature through the glass transition temperature as the Poisson's ratio increases. The behavior of the velocity of transverse wave vs. temperature in the supercooled liquid region could be explained by viscosity...

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

    Science.gov (United States)

    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.

  9. Structural dynamics of supercooled water from quasielastic neutron scattering and molecular simulations.

    Science.gov (United States)

    Qvist, Johan; Schober, Helmut; Halle, Bertil

    2011-04-14

    One of the outstanding challenges presented by liquid water is to understand how molecules can move on a picosecond time scale despite being incorporated in a three-dimensional network of relatively strong H-bonds. This challenge is exacerbated in the supercooled state, where the dramatic slowing down of structural dynamics is reminiscent of the, equally poorly understood, generic behavior of liquids near the glass transition temperature. By probing single-molecule dynamics on a wide range of time and length scales, quasielastic neutron scattering (QENS) can potentially reveal the mechanistic details of water's structural dynamics, but because of interpretational ambiguities this potential has not been fully realized. To resolve these issues, we present here an extensive set of high-quality QENS data from water in the range 253-293 K and a corresponding set of molecular dynamics (MD) simulations to facilitate and validate the interpretation. Using a model-free approach, we analyze the QENS data in terms of two motional components. Based on the dynamical clustering observed in MD trajectories, we identify these components with two distinct types of structural dynamics: picosecond local (L) structural fluctuations within dynamical basins and slower interbasin jumps (J). The Q-dependence of the dominant QENS component, associated with J dynamics, can be quantitatively rationalized with a continuous-time random walk (CTRW) model with an apparent jump length that depends on low-order moments of the jump length and waiting time distributions. Using a simple coarse-graining algorithm to quantitatively identify dynamical basins, we map the newtonian MD trajectory on a CTRW trajectory, from which the jump length and waiting time distributions are computed. The jump length distribution is gaussian and the rms jump length increases from 1.5 to 1.9 Å as the temperature increases from 253 to 293 K. The rms basin radius increases from 0.71 to 0.75 Å over the same range. The

  10. Vibrating-Wire, Supercooled Liquid Water Content Sensor Calibration and Characterization Progress

    Science.gov (United States)

    King, Michael C.; Bognar, John A.; Guest, Daniel; Bunt, Fred

    2016-01-01

    NASA conducted a winter 2015 field campaign using weather balloons at the NASA Glenn Research Center to generate a validation database for the NASA Icing Remote Sensing System. The weather balloons carried a specialized, disposable, vibrating-wire sensor to determine supercooled liquid water content aloft. Significant progress has been made to calibrate and characterize these sensors. Calibration testing of the vibrating-wire sensors was carried out in a specially developed, low-speed, icing wind tunnel, and the results were analyzed. The sensor ice accretion behavior was also documented and analyzed. Finally, post-campaign evaluation of the balloon soundings revealed a gradual drift in the sensor data with increasing altitude. This behavior was analyzed and a method to correct for the drift in the data was developed.

  11. Measurement of Density, Sound Velocity, Surface Tension, and Viscosity of Freely Suspended Supercooled Liquids

    Science.gov (United States)

    Trinh, E. H.

    1995-01-01

    Non-contact methods have been implemented in conjunction with levitation techniques to carry out the measurement of the macroscopic properties of liquids significantly cooled below their nominal melting point. Free suspension of the sample and remote methods allow the deep excursion into the metastable liquid state and the determination of its thermophysical properties. We used this approach to investigate common substances such as water, o-terphenyl, succinonitrile, as well as higher temperature melts such as molten indium, aluminum and other metals. Although these techniques have thus far involved ultrasonic, electromagnetic, and more recently electrostatic levitation, we restrict our attention to ultrasonic methods in this paper. The resulting magnitude of maximum thermal supercooling achieved have ranged between 10 and 15% of the absolute temperature of the melting point for the materials mentioned above. The physical properties measurement methods have been mostly novel approaches, and the typical accuracy achieved have not yet matched their standard equivalent techniques involving contained samples and invasive probing. They are currently being refined, however, as the levitation techniques become more widespread, and as we gain a better understanding of the physics of levitated liquid samples.

  12. Structural stability of Pd40Cu30Ni10P20 metallic glass in supercooled liquid region

    International Nuclear Information System (INIS)

    Jiang, J.Z.; Saksl, K.

    2004-01-01

    Phase separation of bulk and ribbon Pd 40 Cu 30 Ni 10 P 20 glasses, annealed in the supercooled liquid region at ambient pressure and high pressures, has been studied by means of differential scanning calorimetry (DSC) and X-ray diffraction techniques. DSC measurements show only one glass transition event in all annealed samples, indicating that no phase separation occurs in the alloy annealed in the supercooled liquid region. Phase analyses reveal at least six crystalline phases in the crystallized sample: monoclinic, tetragonal Cu 3 Pd-like, rhombohedral, fcc-Ni 2 Pd 2 P, fcc-(Ni, Pd) solid solution, and body-centered tetragonal (bct) Ni 3 P-like phases. Annealing treatments under external pressures in the vicinity of the glass transition temperature neither induce phase separation nor alter the glass transition temperature of the Pd 40 Cu 30 Ni 10 P 20 bulk glass

  13. Mobility of supercooled liquid toluene, ethylbenzene, and benzene near their glass transition temperatures investigated using inert gas permeation.

    Science.gov (United States)

    May, R Alan; Smith, R Scott; Kay, Bruce D

    2013-11-21

    We investigate the mobility of supercooled liquid toluene, ethylbenzene, and benzene near their respective glass transition temperatures (Tg). The permeation rate of Ar, Kr, and Xe through the supercooled liquid created when initially amorphous overlayers are heated above their glass transition temperature is used to determine the diffusivity. Amorphous benzene crystallizes at temperatures well below its Tg, and as a result, the inert gas underlayer remains trapped until the onset of benzene desorption. In contrast, for toluene and ethylbenzene the onset of inert gas permeation is observed at temperatues near Tg. The inert gas desorption peak temperature as a function of the heating rate and overlayer thickness is used to quantify the diffusivity of supercooled liquid toluene and ethylbenzene from 115 to 135 K. In this temperature range, diffusivities are found to vary across 5 orders of magnitude (∼10(-14) to 10(-9) cm(2)/s). The diffusivity data are compared to viscosity measurements and reveal a breakdown in the Stokes-Einstein relationship at low temperatures. However, the data are well fit by the fractional Stokes-Einstein equation with an exponent of 0.66. Efforts to determine the diffusivity of a mixture of benzene and ethylbenzene are detailed, and the effect of mixing these materials on benzene crystallization is explored using infrared spectroscopy.

  14. New Scenario of Dynamical Heterogeneity in Supercooled Liquid and Glassy States of 2D Monatomic System.

    Science.gov (United States)

    Van Hoang, Vo; Teboul, Victor; Odagaki, Takashi

    2015-12-24

    Via analysis of spatiotemporal arrangements of atoms based on their dynamics in supercooled liquid and glassy states of a 2D monatomic system with a double-well Lennard-Jones-Gauss (LJG) interaction potential, we find a new scenario of dynamical heterogeneity. Atoms with the same or very close mobility have a tendency to aggregate into clusters. The number of atoms with high mobility (and size of their clusters) increases with decreasing temperature passing over a maximum before decreasing down to zero. Position of the peak moves toward a lower temperature if mobility of atoms in clusters is lower together with an enhancement of height of the peak. In contrast, the number of atoms with very low mobility or solidlike atoms (and size of their clusters) has a tendency to increase with decreasing temperature and then it suddenly increases in the vicinity of the glass transition temperature leading to the formation of a glassy state. A sudden increase in the number of strongly correlated solidlike atoms in the vicinity of a glass transition temperature (Tg) may be an origin of a drastical increase in viscosity of the glass-forming systems approaching the glass transition. In fact, we find that the diffusion coefficient decays exponentially with a fraction of solidlike atoms exhibiting a sudden decrease in the vicinity of the glass transition region.

  15. Ionic and Molecular Liquids

    DEFF Research Database (Denmark)

    Chaban, Vitaly V.; Prezhdo, Oleg

    2013-01-01

    applications of RTILs in combination with molecular liquids, concentrating on three significant areas: (1) the use of molecular liquids to decrease the viscosity of RTILs; (2) the role of RTIL micelle formation in water and organic solvents; and (3) the ability of RTILs to adsorb pollutant gases. Current...

  16. Two-Order-Parameter Description of Liquids: Critical Phenomena and Phase Separation of Supercooled Liquids

    OpenAIRE

    Tanaka, Hajime

    1997-01-01

    Because of the isotropic and disordered nature of liquids, the anisotropy hidden in intermolecular interactions are often neglected. Accordingly, the order parameter describing a simple liquid has so far been believed to be only density. In contrast to this common sense, we propose that two order parameters, namely, density and bond order parameters, are required to describe the phase behavior of liquids since they intrinsically tend to form local bonds. This model gives us clear physical exp...

  17. Metastable liquid-liquid transition in a molecular model of water

    Science.gov (United States)

    Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang; Car, Roberto; Panagiotopoulos, Athanassios Z.; Debenedetti, Pablo G.

    2014-06-01

    Liquid water's isothermal compressibility and isobaric heat capacity, and the magnitude of its thermal expansion coefficient, increase sharply on cooling below the equilibrium freezing point. Many experimental, theoretical and computational studies have sought to understand the molecular origin and implications of this anomalous behaviour. Of the different theoretical scenarios put forward, one posits the existence of a first-order phase transition that involves two forms of liquid water and terminates at a critical point located at deeply supercooled conditions. Some experimental evidence is consistent with this hypothesis, but no definitive proof of a liquid-liquid transition in water has been obtained to date: rapid ice crystallization has so far prevented decisive measurements on deeply supercooled water, although this challenge has been overcome recently. Computer simulations are therefore crucial for exploring water's structure and behaviour in this regime, and have shown that some water models exhibit liquid-liquid transitions and others do not. However, recent work has argued that the liquid-liquid transition has been mistakenly interpreted, and is in fact a liquid-crystal transition in all atomistic models of water. Here we show, by studying the liquid-liquid transition in the ST2 model of water with the use of six advanced sampling methods to compute the free-energy surface, that two metastable liquid phases and a stable crystal phase exist at the same deeply supercooled thermodynamic condition, and that the transition between the two liquids satisfies the thermodynamic criteria of a first-order transition. We follow the rearrangement of water's coordination shell and topological ring structure along a thermodynamically reversible path from the low-density liquid to cubic ice. We also show that the system fluctuates freely between the two liquid phases rather than crystallizing. These findings provide unambiguous evidence for a liquid-liquid transition in

  18. Nature of the anomalies in the supercooled liquid state of the mW model of water

    Science.gov (United States)

    Holten, Vincent; Limmer, David T.; Molinero, Valeria; Anisimov, Mikhail A.

    2013-05-01

    The thermodynamic properties of the supercooled liquid state of the mW model of water show anomalous behavior. Like in real water, the heat capacity and compressibility sharply increase upon supercooling. One of the possible explanations of these anomalies, the existence of a second (liquid-liquid) critical point, is not supported by simulations for this model. In this work, we reproduce the anomalies of the mW model with two thermodynamic scenarios: one based on a non-ideal "mixture" with two different types of local order of the water molecules, and one based on weak crystallization theory. We show that both descriptions accurately reproduce the model's basic thermodynamic properties. However, the coupling constant required for the power laws implied by weak crystallization theory is too large relative to the regular backgrounds, contradicting assumptions of weak crystallization theory. Fluctuation corrections outside the scope of this work would be necessary to fit the forms predicted by weak crystallization theory. For the two-state approach, the direct computation of the low-density fraction of molecules in the mW model is in agreement with the prediction of the phenomenological equation of state. The non-ideality of the "mixture" of the two states never becomes strong enough to cause liquid-liquid phase separation, also in agreement with simulation results.

  19. Nature of the anomalies in the supercooled liquid state of the mW model of water.

    Science.gov (United States)

    Holten, Vincent; Limmer, David T; Molinero, Valeria; Anisimov, Mikhail A

    2013-05-07

    The thermodynamic properties of the supercooled liquid state of the mW model of water show anomalous behavior. Like in real water, the heat capacity and compressibility sharply increase upon supercooling. One of the possible explanations of these anomalies, the existence of a second (liquid-liquid) critical point, is not supported by simulations for this model. In this work, we reproduce the anomalies of the mW model with two thermodynamic scenarios: one based on a non-ideal "mixture" with two different types of local order of the water molecules, and one based on weak crystallization theory. We show that both descriptions accurately reproduce the model's basic thermodynamic properties. However, the coupling constant required for the power laws implied by weak crystallization theory is too large relative to the regular backgrounds, contradicting assumptions of weak crystallization theory. Fluctuation corrections outside the scope of this work would be necessary to fit the forms predicted by weak crystallization theory. For the two-state approach, the direct computation of the low-density fraction of molecules in the mW model is in agreement with the prediction of the phenomenological equation of state. The non-ideality of the "mixture" of the two states never becomes strong enough to cause liquid-liquid phase separation, also in agreement with simulation results.

  20. Fe-based bulk metallic glasses with a larger supercooled liquid region and high ductility

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, K.Q. [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110178 (China)], E-mail: kqqiu@yahoo.com.cn; Pang, J.; Ren, Y.L.; Zhang, H.B. [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110178 (China); Ma, C.L.; Zhang, T. [School of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics, Beijing 100083 (China)

    2008-12-20

    Bulk metallic glasses (BMGs) with compositions of Fe{sub 61.5-x}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}M{sub x} (x = 2, 3; M = Ni, Nb) were fabricated by copper mold casting using raw industrial materials. The X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical tester and scanning electron microscope (SEM) were employed to check the phase constituent, the thermal stability, the mechanical properties and the fracture surfaces of as-cast samples. The results indicate that the BMGs with diameters of 1.5-3 mm were fabricated for the alloys investigated. The largest supercooled liquid region (SLR) up to 76 K was found for Fe{sub 58.5}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}Ni{sub 3} BMG. The BMGs with Ni addition exhibit not only high fracture strengths reaching 3770 MPa for x = 2 and 3980 MPa for x = 3 alloys, respectively, but also apparently plastic strains up to 0.67% and 0.93%, respectively. The fracture surfaces of the Fe{sub 61.5-x}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}Ni{sub x} (x = 2, 3) alloys with plasticity show narrow ridges characteristic of venous patterns combining with tearing flow between the ridges. While the Nb containing alloys show not only a lower SLR below 60 K but also a lower stress below 2400 MPa, as well as almost no plastic strain before fracture.

  1. Communication: Towards first principles theory of relaxation in supercooled liquids formulated in terms of cooperative motion.

    Science.gov (United States)

    Freed, Karl F

    2014-10-14

    A general theory of the long time, low temperature dynamics of glass-forming fluids remains elusive despite the almost 20 years since the famous pronouncement by the Nobel Laureate P. W. Anderson, "The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition" [Science 267, 1615 (1995)]. While recent work indicates that Adam-Gibbs theory (AGT) provides a framework for computing the structural relaxation time of supercooled fluids and for analyzing the properties of the cooperatively rearranging dynamical strings observed in low temperature molecular dynamics simulations, the heuristic nature of AGT has impeded general acceptance due to the lack of a first principles derivation [G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965)]. This deficiency is rectified here by a statistical mechanical derivation of AGT that uses transition state theory and the assumption that the transition state is composed of elementary excitations of a string-like form. The strings are assumed to form in equilibrium with the mobile particles in the fluid. Hence, transition state theory requires the strings to be in mutual equilibrium and thus to have the size distribution of a self-assembling system, in accord with the simulations and analyses of Douglas and co-workers. The average relaxation rate is computed as a grand canonical ensemble average over all string sizes, and use of the previously determined relation between configurational entropy and the average cluster size in several model equilibrium self-associating systems produces the AGT expression in a manner enabling further extensions and more fundamental tests of the assumptions.

  2. Communication: Towards first principles theory of relaxation in supercooled liquids formulated in terms of cooperative motion

    Energy Technology Data Exchange (ETDEWEB)

    Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute and Department of Chemistry, University of Chicago, 929 East 57 Street, Chicago, Illinois 60637 (United States)

    2014-10-14

    A general theory of the long time, low temperature dynamics of glass-forming fluids remains elusive despite the almost 20 years since the famous pronouncement by the Nobel Laureate P. W. Anderson, “The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition” [Science 267, 1615 (1995)]. While recent work indicates that Adam-Gibbs theory (AGT) provides a framework for computing the structural relaxation time of supercooled fluids and for analyzing the properties of the cooperatively rearranging dynamical strings observed in low temperature molecular dynamics simulations, the heuristic nature of AGT has impeded general acceptance due to the lack of a first principles derivation [G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965)]. This deficiency is rectified here by a statistical mechanical derivation of AGT that uses transition state theory and the assumption that the transition state is composed of elementary excitations of a string-like form. The strings are assumed to form in equilibrium with the mobile particles in the fluid. Hence, transition state theory requires the strings to be in mutual equilibrium and thus to have the size distribution of a self-assembling system, in accord with the simulations and analyses of Douglas and co-workers. The average relaxation rate is computed as a grand canonical ensemble average over all string sizes, and use of the previously determined relation between configurational entropy and the average cluster size in several model equilibrium self-associating systems produces the AGT expression in a manner enabling further extensions and more fundamental tests of the assumptions.

  3. Mixed quantum/classical approach to OH-stretch inelastic incoherent neutron scattering spectroscopy for ambient and supercooled liquid water and ice Ih

    Energy Technology Data Exchange (ETDEWEB)

    Shi, L.; Skinner, J. L. [Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706 (United States)

    2015-07-07

    OH-stretch inelastic incoherent neutron scattering (IINS) has been measured to determine the vibrational density of states (VDOS) in the OH-stretch region for liquid water, supercooled water, and ice Ih, providing complementary information to IR and Raman spectroscopies about hydrogen bonding in these phases. In this work, we extend the combined electronic-structure/molecular-dynamics (ES/MD) method, originally developed by Skinner and co-workers to simulate OH-stretch IR and Raman spectra, to the calculation of IINS spectra with small k values. The agreement between theory and experiment in the limit k → 0 is reasonable, further validating the reliability of the ES/MD method in simulating OH-stretch spectroscopy in condensed phases. The connections and differences between IINS and IR spectra are analyzed to illustrate the advantages of IINS over IR in estimating the OH-stretch VDOS.

  4. Mixed quantum/classical approach to OH-stretch inelastic incoherent neutron scattering spectroscopy for ambient and supercooled liquid water and ice Ih

    International Nuclear Information System (INIS)

    Shi, L.; Skinner, J. L.

    2015-01-01

    OH-stretch inelastic incoherent neutron scattering (IINS) has been measured to determine the vibrational density of states (VDOS) in the OH-stretch region for liquid water, supercooled water, and ice Ih, providing complementary information to IR and Raman spectroscopies about hydrogen bonding in these phases. In this work, we extend the combined electronic-structure/molecular-dynamics (ES/MD) method, originally developed by Skinner and co-workers to simulate OH-stretch IR and Raman spectra, to the calculation of IINS spectra with small k values. The agreement between theory and experiment in the limit k → 0 is reasonable, further validating the reliability of the ES/MD method in simulating OH-stretch spectroscopy in condensed phases. The connections and differences between IINS and IR spectra are analyzed to illustrate the advantages of IINS over IR in estimating the OH-stretch VDOS

  5. Ionic and Molecular Liquids

    DEFF Research Database (Denmark)

    Chaban, Vitaly V.; Prezhdo, Oleg

    2013-01-01

    Because of their outstanding versatility, room-temperature ionic liquids (RTILs) are utilized in an ever increasing number of novel and fascinating applications, making them the Holy Grail of modern materials science. In this Perspective, we address the fundamental research and prospective...... applications of RTILs in combination with molecular liquids, concentrating on three significant areas: (1) the use of molecular liquids to decrease the viscosity of RTILs; (2) the role of RTIL micelle formation in water and organic solvents; and (3) the ability of RTILs to adsorb pollutant gases. Current...

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

    Directory of Open Access Journals (Sweden)

    Hua Tong

    2018-03-01

    Full Text Available 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 ξ_{4}, when t reaches the relaxation time τ_{α}. 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∼ξ_{4}, indicating that the static length ξ grows coherently with the dynamic one ξ_{4} upon cooling. This further suggests an intrinsic link between τ_{α} 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

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

    Science.gov (United States)

    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

  8. An apparatus with a horizontal capillary tube intended for measurement of the surface tension of supercooled liquids

    Science.gov (United States)

    Vinš, Václav; Hošek, Jan; Hykl, Jiří; Hrubý, Jan

    2015-05-01

    New experimental apparatus for measurement of the surface tension of liquids under the metastable supercooled state has been designed and assembled in the study. The measuring technique is similar to the method employed by P.T. Hacker [NACA TN 2510] in 1951. A short liquid thread of the liquid sample was sucked inside a horizontal capillary tube partly placed in a temperature-controlled glass chamber. One end of the capillary tube was connected to a setup with inert gas which allowed for precise tuning of the gas overpressure in order of hundreds of Pa. The open end of the capillary tube was precisely grinded and polished before the measurement in order to assure planarity and perpendicularity of the outer surface. The liquid meniscus at the open end was illuminated by a laser beam and observed by a digital camera. Application of an increasing overpressure of the inert gas at the inner meniscus of the liquid thread caused variation of the outer meniscus such that it gradually changed from concave to flat and subsequently convex shape. The surface tension at the temperature of the inner meniscus could be evaluated from the overpressure corresponding to exactly planar outer meniscus. Detailed description of the new setup together with results of the preliminary tests is provided in the study.

  9. Time scales of supercooled water and implications for reversible polyamorphism

    Science.gov (United States)

    Limmer, David T.; Chandler, David

    2015-09-01

    Deeply supercooled water exhibits complex dynamics with large density fluctuations, ice coarsening and characteristic time scales extending from picoseconds to milliseconds. Here, we discuss implications of these time scales as they pertain to two-phase coexistence and to molecular simulations of supercooled water. Specifically, we argue that it is possible to discount liquid-liquid criticality because the time scales imply that correlation lengths for such behaviour would be bounded by no more than a few nanometres. Similarly, it is possible to discount two-liquid coexistence because the time scales imply a bounded interfacial free energy that cannot grow in proportion to a macroscopic surface area. From time scales alone, therefore, we see that coexisting domains of differing density in supercooled water can be no more than nanoscale transient fluctuations.

  10. Supercooled smectic nanoparticles

    DEFF Research Database (Denmark)

    Kuntsche, Judith; Westesen, K; Drechsler, M

    2004-01-01

    The possibility of preparing nanoparticles in the supercooled thermotropic liquid crystalline state from cholesterol esters with saturated acyl chains as well as the incorporation of model drugs into the dispersions was investigated using cholesteryl myristate (CM) as a model cholesterol ester....

  11. Glass transition memorized by the enthalpy-entropy compensation in the shear thinning of supercooled metallic liquids

    Science.gov (United States)

    Zhang, Meng; Liu, Lin

    2018-06-01

    To unravel the true nature of glass transition, broader insights into glass forming have been gained by examining the stress-driven glassy systems, where strong shear thinning, i.e. a reduced viscosity under increasing shear rate, is encountered. It is argued that arbitrarily small stress-driven shear rates would ‘melt’ the glass and erase any memory of its thermal history. In this work, we report a glass transition memorized by the enthalpy-entropy compensation in strongly shear-thinned supercooled metallic liquids, which coincides with the thermal glass transition in both the transition temperature and the activation Gibbs free energy. Our findings provide distinctive insights into both glass forming and shear thinning, and enrich current knowledge on the ubiquitous enthalpy-entropy compensation empirical law in condensed matter physics.

  12. Evidence for a liquid-liquid critical point in supercooled water within the E3B3 model and a possible interpretation of the kink in the homogeneous nucleation line

    Energy Technology Data Exchange (ETDEWEB)

    Ni, Yicun; Skinner, J. L. [Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706 (United States)

    2016-06-07

    Supercooled water exhibits many thermodynamic anomalies, and several scenarios have been proposed to interpret them, among which the liquid-liquid critical point (LLCP) hypothesis is the most commonly discussed. We investigated Widom lines and the LLCP of deeply supercooled water, by using molecular dynamics simulation with a newly reparameterized water model that explicitly includes three-body interactions. Seven isobars are studied from ambient pressure to 2.5 kbar, and Widom lines are identified by calculating maxima in the coefficient of thermal expansion and the isothermal compressibility (both with respect to temperature). From these data we estimate that the LLCP of the new water model is at 180 K and 2.1 kbar. The oxygen radial distribution function is calculated along the 2 kbar isobar. It shows a steep change in the height of its second peak between 180 and 185 K, which indicates a transition between the high-density liquid and low-density liquid phases and which is consistent with the ascribed location of the critical point. The good agreement of the height of the second peak of the radial distribution function between simulation and experiment at 1 bar, as a function of temperature, supports the validity of the model. The location of the LLCP within the model is close to the kink in the experimental homogeneous nucleation line. We use existing experimental data to argue that the experimental LLCP is at 168 K and 1.95 kbar and speculate how this LLCP and its Widom line might be responsible for the kink in the homogeneous nucleation line.

  13. More accurate X-ray scattering data of deeply supercooled bulk liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Neuefeind, Joerg C [ORNL; Benmore, Chris J [Argonne National Laboratory (ANL); Weber, Richard [Argonne National Laboratory (ANL); Paschek, Dietmar [Rostock University, Rostock, Germany

    2011-01-01

    Deeply supercooled water droplets held container-less in an acoustic levitator are investigated with high energy X-ray scattering. The temperature dependence X-ray structure function is found to be non-linear. Comparison with two popular computer models reveals that structural changes are predicted too abrupt by the TIP5P model, while the rate of change predicted by TIP4P is in much better agreement with experiment. The abrupt structural changes predicted by the TIP5P model to occur in the temperature range between 260-240K as water approaches the homogeneous nucleation limit are unrealistic. Both models underestimate the distance between neighbouring oxygen atoms and overestimate the sharpness of the OO distance distribution, indicating that the strength of the H-bond is overestimated in these models.

  14. The kinetic glass transition of the Zr46.75Ti8.25Cu7.5Ni10Be27.5 bulk metallic glass former-supercooled liquids on a long time scale

    International Nuclear Information System (INIS)

    Busch, R.; Johnson, W.L.

    1998-01-01

    Viscosity and enthalpy relaxation from the amorphous state into the supercooled liquid state was investigated in the bulk metallic glass forming Zr 46.75 Ti 8.25 Cu 7.5 Ni 10 Be 27.5 alloy below the calorimetric glass transition. At different temperatures, the viscosities relax into states that obey the same Vogel endash Fulcher endash Tammann relation as the data obtained at higher temperatures in the supercooled liquid. Enthalpy recovery experiments after relaxation in the same temperature range show that the enthalpy of the material reaches values that also corresponds to the supercooled liquid state. The glass relaxes into a metastable supercooled liquid state, if it is observed on a long time scale. Equilibration is possible far below the calorimetric glass transition and very likely even below the isentropic temperature. copyright 1998 American Institute of Physics

  15. Externally predictive quantitative modeling of supercooled liquid vapor pressure of polychlorinated-naphthalenes through electron-correlation based quantum-mechanical descriptors.

    Science.gov (United States)

    Vikas; Chayawan

    2014-01-01

    For predicting physico-chemical properties related to environmental fate of molecules, quantitative structure-property relationships (QSPRs) are valuable tools in environmental chemistry. For developing a QSPR, molecular descriptors computed through quantum-mechanical methods are generally employed. The accuracy of a quantum-mechanical method, however, rests on the amount of electron-correlation estimated by the method. In this work, single-descriptor QSPRs for supercooled liquid vapor pressure of chloronaphthalenes and polychlorinated-naphthalenes are developed using molecular descriptors based on the electron-correlation contribution of the quantum-mechanical descriptor. The quantum-mechanical descriptors for which the electron-correlation contribution is analyzed include total-energy, mean polarizability, dipole moment, frontier orbital (HOMO/LUMO) energy, and density-functional theory (DFT) based descriptors, namely, absolute electronegativity, chemical hardness, and electrophilicity index. A total of 40 single-descriptor QSPRs were developed using molecular descriptors computed with advanced semi-empirical (SE) methods, namely, RM1, PM7, and ab intio methods, namely, Hartree-Fock and DFT. The developed QSPRs are validated using state-of-the-art external validation procedures employing an external prediction set. From the comparison of external predictivity of the models, it is observed that the single-descriptor QSPRs developed using total energy and correlation energy are found to be far more robust and predictive than those developed using commonly employed descriptors such as HOMO/LUMO energy and dipole moment. The work proposes that if real external predictivity of a QSPR model is desired to be explored, particularly, in terms of intra-molecular interactions, correlation-energy serves as a more appropriate descriptor than the polarizability. However, for developing QSPRs, computationally inexpensive advanced SE methods such as PM7 can be more reliable than

  16. An energy landscape based approach for studying supercooled liquid and glassy thin films

    Science.gov (United States)

    Shah, Pooja; Mittal, Jeetain; Truskett, Thomas M.

    2004-03-01

    Materials in confined spaces are important in science and technology. Examples include biological fluids in membranes, liquids trapped in porous rocks, and thin-film materials used in high-resolution patterning technologies. However, few reliable rules exist to predict how the properties of materials will be affected by thin-film confinement. We have recently shown that the potential energy landscape formalism can be used to study, by both theory [1] and simulation [2], how the behavior of thin-film materials depends on sample dimensions and film-substrate interactions. Our landscape-based mean-field theory [1] can be used to study both the thermodynamic properties and the ideal glass transition of thin films. It predicts that, in the case of neutral or repulsive walls, the ideal glass transition temperature is lowered by decreasing film thickness. This is in qualitative agreement with experimental trends for the kinetic glass transition in confined fluids. Landscape-based approaches are also valuable for understanding the structural and mechanical properties of thin-film glasses. We demonstrate how the concept of an "equation of state of the energy landscape" [3] can be generalized to thin films [1, 2], where it gives insights into potential molecular mechanisms of tensile strength. [1] T. M. Truskett and V. Ganesan, J. Chem. Phys. 119, 1897-1900(2003); J. Mittal, P. Shah and T. M. Truskett, to be submitted to Langmuir. [2] P. Shah and T. M. Truskett, to be submitted to J. Phys. Chem. B. [3] S. Sastry, P. G. Debenedetti and F. H. Stillinger, Phys. Rev. E 56, 5533 (1997)

  17. Pressure effect on crystallization of metallic glass Fe72P11C6Al5B4Ga2 alloy with wide supercooled liquid region

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Olsen, J. S.; Gerward, Leif

    2000-01-01

    The effect of pressure on the crystallization behavior of metallic glass Fe72P11C6Al5B4Ga2 alloy with a wide supercooled liquid region has been investigated by in situ high-pressure and high-temperature x-ray diffraction measurements using synchrotron radiation. In the pressure range from 0 to 2...... mobility and changes of the Gibbs free energy of various phases with pressure. ©2000 American Institute of Physics....

  18. Air oxidation of Zr65Cu17.5Ni10Al7.5 in its amorphous and supercooled liquid states, studied by thermogravimetric analysis

    International Nuclear Information System (INIS)

    Dhawan, A.; Sharma, S.K.; Raetzke, K.; Faupel, F.

    2003-01-01

    The oxidation behaviour of the bulk amorphous alloy Zr 65 Cu 17.5 Ni 10 Al 7.5 was studied in air at various temperatures in the temperature range 591-732 K using a thermogravimetric analyser (TGA). The oxidation kinetics of the alloy obeys the parabolic rate law showing two different linear regions (in the plots of mass gain versus square root of oxidation time) which are attributed to the amorphous and the supercooled liquid states of the alloy. The value of the activation energy Q for the amorphous state as calculated from the temperature dependence of the rate constants is found to be 1.80±0.1 eV and the corresponding value obtained for the supercooled liquid state is 1.20±0.1 eV. It is suggested that the rate controlling process during oxidation of the amorphous state is the back-diffusion of Ni, and possibly Cu also, while the oxidation in the supercooled liquid state is dominated by the inward diffusion of oxygen. (copyright 2003 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

    Science.gov (United States)

    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.

  20. Supercooled dynamics of glass-forming liquids and polymers under hydrostatic pressure

    Energy Technology Data Exchange (ETDEWEB)

    Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Hensel-Bielowka, S [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Paluch, M [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Casalini, R [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Chemistry Department, George Mason University, Fairfax, VA 22030 (United States)

    2005-06-01

    An intriguing problem in condensed matter physics is understanding the glass transition, in particular the dynamics in the equilibrium liquid close to vitrification. Recent advances have been made by using hydrostatic pressure as an experimental variable. These results are reviewed, with an emphasis in the insight provided into the mechanisms underlying the relaxation properties of glass-forming liquids and polymers.

  1. Supercooled liquid vapour pressures and related thermodynamic properties of polycyclic aromatic hydrocarbons determined by gas chromatography

    NARCIS (Netherlands)

    Haftka, J.J.H.; Parsons, J.R.; Govers, H.A.J.

    2006-01-01

    A gas chromatographic method using Kovats retention indices has been applied to determine the liquid vapour pressure (P-i), enthalpy of vaporization (Delta H-i) and difference in heat capacity between gas and liquid phase (Delta C-i) for a group of polycyclic aromatic hydrocarbons (PAHs). This group

  2. Using Peltier Cells to Study Solid-Liquid-Vapour Transitions and Supercooling

    Science.gov (United States)

    Torzo, Giacomo; Soletta, Isabella; Branca, Mario

    2007-01-01

    We propose an apparatus for teaching experimental thermodynamics in undergraduate introductory courses, using thermoelectric modules and a real-time data acquisition system. The device may be made at low cost, still providing an easy approach to the investigation of liquid-solid and liquid-vapour phase transitions and of metastable states…

  3. Investigation of crystallization kinetics and deformation behavior in supercooled liquid region of CuZr-based bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ke; Fan, Xinhui; Li, Bing; Li, Yanhong; Wang, Xin; Xu, Xuanxuan [Xi' an Technological Univ. (China). School of Material and Chemical Engineering

    2017-08-15

    In this paper, a systematic study of crystallization kinetics and deformation behavior is presented for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} bulk metallic glass in the supercooled liquid region. Crystallization results showed that the activation energy for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} was calculated using the Arrhenius equation in isothermal mode and the Kissinger-Akahira-Sunose method in non-isothermal mode. The activation energy was quite high compared with other bulk metallic glasses. Based on isothermal transformation kinetics described by the Johson-Mehl-Avrami model, the average Avrami exponent of about 3.05 implies a mainly diffusion controlled three-dimensional growth with an increasing nucleation rate during the crystallization. For warm deformation, the results showed that deformation behavior, composed of homogeneous and inhomogeneous deformation, is strongly dependent on strain rate and temperature. The homogeneous deformation transformed from non-Newtonian flow to Newtonian flow with a decrease in strain rate and an increase in temperature. It was found that the crystallization during high temperature deformation is induced by heating. The appropriate working temperature/strain rate combination for the alloy forming, without in-situ crystallization, was deduced by constructing an empirical deformation map. The optimum process condition for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} can be expressed as T∝733 K and ∝ ε 10{sup -3} s{sup -1}.

  4. Fragile to strong crossover at the Widom line in supercooled aqueous solutions of NaCl

    Energy Technology Data Exchange (ETDEWEB)

    Gallo, P. [Dipartimento di Matematica e Fisica, Università Roma Tre, Via della Vasca Navale 84, I-00146 Rome, Italy and INFN, Sezione di Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy); Corradini, D.; Rovere, M., E-mail: rovere@fis.uniroma3.it [Dipartimento di Matematica e Fisica, Università Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy)

    2013-11-28

    We study by molecular dynamics simulations the dynamical properties of an aqueous solution of NaCl at a concentration of 0.67 mol/kg upon supercooling. In a previous study of the same ionic solution, we have located the liquid-liquid critical point (LLCP) and determined the Widom line connected to the liquid-liquid transition. We present here the results obtained from the study of the self-intermediate scattering function in a large range of temperatures and densities approaching the LLCP. The structural relaxation is in agreement with the mode coupling theory (MCT) in the region of mild supercooling. In the deeper supercooled region the α-relaxation time as function of temperature deviates from the MCT power law prediction showing a crossover from a fragile to a strong behavior. This crossover is found upon crossing the Widom line. The same trend was found in bulk water upon supercooling and it appears almost unchanged by the interaction with ions apart from a shift in the thermodynamic plane toward lower pressures and higher temperatures. These results show that the phenomenology of supercooled water transfers from bulk to solution where the study of the supercooled region is experimentally less difficult.

  5. Equilibrium and out-of-equilibrium thermodynamics in supercooled liquids and glasses

    International Nuclear Information System (INIS)

    Mossa, S; Nave, E La; Tartaglia, P; Sciortino, F

    2003-01-01

    We review the inherent structure thermodynamical formalism and the formulation of an equation of state (EOS) for liquids in equilibrium based on the (volume) derivatives of the statistical properties of the potential energy surface. We also show that, under the hypothesis that during ageing the system explores states associated with equilibrium configurations, it is possible to generalize the proposed EOS to out-of-equilibrium (OOE) conditions. The proposed formulation is based on the introduction of one additional parameter which, in the chosen thermodynamic formalism, can be chosen as the local minimum where the slowly relaxing OOE liquid is trapped

  6. Dynamics of supercooled liquids: excess wings, β peaks, and rotation-translation coupling

    International Nuclear Information System (INIS)

    Cummins, H Z

    2005-01-01

    Dielectric susceptibility spectra of liquids cooled towards the liquid-glass transition often exhibit secondary structure in the frequency region between the α peak and the susceptibility minimum, in the form of either an 'excess wing' or a secondary peak-the Johari-Goldstein β peak. Recently, Goetze and Sperl (2004 Phys. Rev. Lett. 92 105701) showed that a simple schematic mode coupling theory model, which incorporates rotation-translation (RT) coupling, successfully describes the nearly logarithmic decay observed in optical Kerr effect data. This model also exhibits both excess wing and β peak features, qualitatively resembling experimental dielectric data. It also predicts that the excess wing slope decreases with decreasing temperature and gradually evolves into a β peak with increasing RT coupling. We therefore suggest that these features and their observed evolution with temperature may be consequences of RT coupling

  7. Scaling parallels in the non-Debye dielectric relaxation of ionic glasses and dipolar supercooled liquids

    International Nuclear Information System (INIS)

    Sidebottom, D.L.; Green, P.F.; Brow, R.K.

    1997-01-01

    We compare the dielectric response of ionic glasses and dipolar liquids near the glass transition. Our work is divided into two parts. In the first section we examine ionic glasses and the two prominent approaches to analyzing the dielectric response. The conductivity of ion-conducting glasses displays a power law dispersion σ(ω)∝ω n , where n∼0.67, but frequently the dielectric response is analyzed using the electrical modulus M * (ω)=1/var-epsilon * (ω), where var-epsilon * (ω)=var-epsilon(ω)-iσ(ω)/ω is the complex permittivity. We reexamine two specific examples where the shape of M * (ω) changes in response to changes in (a) temperature and (b) ion concentration, to suggest fundamental changes in ion dynamics are occurring. We show, however, that these changes in the shape of M * (ω) occur in the absence of changes in the scaling properties of σ(ω), for which n remains constant. In the second part, we examine the dielectric relaxation found in dipolar liquids, for which var-epsilon * (ω) likewise exhibits changes in shape on approach to the glass transition. Guided by similarities of M * (ω) in ionic glasses and var-epsilon * (ω) in dipolar liquids, we demonstrate that a recent scaling approach proposed by Dixon and co-workers for var-epsilon * (ω) of dipolar relaxation also appears valid for M * (ω) in the ionic case. While this suggests that the Dixon scaling approach is more universal than previously recognized, we demonstrate how the dielectric response can be scaled in a linear manner using an alternative data representation. copyright 1997 The American Physical Society

  8. Supercooled liquid vapour pressures and related thermodynamic properties of polycyclic aromatic hydrocarbons determined by gas chromatography.

    Science.gov (United States)

    Haftka, Joris J H; Parsons, John R; Govers, Harrie A J

    2006-11-24

    A gas chromatographic method using Kováts retention indices has been applied to determine the liquid vapour pressure (P(i)), enthalpy of vaporization (DeltaH(i)) and difference in heat capacity between gas and liquid phase (DeltaC(i)) for a group of polycyclic aromatic hydrocarbons (PAHs). This group consists of 19 unsubstituted, methylated and sulphur containing PAHs. Differences in log P(i) of -0.04 to +0.99 log units at 298.15K were observed between experimental values and data from effusion and gas saturation studies. These differences in log P(i) have been fitted with multilinear regression resulting in a compound and temperature dependent correction. Over a temperature range from 273.15 to 423.15K, differences in corrected log P(i) of a training set (-0.07 to +0.03 log units) and a validation set (-0.17 to 0.19 log units) were within calculated error ranges. The corrected vapour pressures also showed a good agreement with other GC determined vapour pressures (average -0.09 log units).

  9. Configurational entropy measurements in extremely supercooled liquids that break the glass ceiling

    Science.gov (United States)

    Berthier, Ludovic; Charbonneau, Patrick; Coslovich, Daniele; Ninarello, Andrea; Ozawa, Misaki; Yaida, Sho

    2017-10-01

    Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, because of the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally relevant timescales. In this work, we not only close the colossal gap between experiments and simulations but manage to create in silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four estimates of their configurational entropy. These measurements consistently confirm that the steep entropy decrease observed in experiments is also found in simulations, even beyond the experimental glass transition. Our numerical results thus extend the observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

  10. Breaking the glass ceiling: Configurational entropy measurements in extremely supercooled liquids

    Science.gov (United States)

    Berthier, Ludovic

    Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, due to the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally-relevant timescales. In this work we not only close the colossal gap between experiments and simulations but manage to create in-silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four independent estimates of their configurational entropy. These measurements consistently indicate that the steep entropy decrease observed in experiments is found in simulations even beyond the experimental glass transition. Our numerical results thus open a new observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

  11. Thermal conductivity of supercooled water.

    Science.gov (United States)

    Biddle, John W; Holten, Vincent; Sengers, Jan V; Anisimov, Mikhail A

    2013-04-01

    The heat capacity of supercooled water, measured down to -37°C, shows an anomalous increase as temperature decreases. The thermal diffusivity, i.e., the ratio of the thermal conductivity and the heat capacity per unit volume, shows a decrease. These anomalies may be associated with a hypothesized liquid-liquid critical point in supercooled water below the line of homogeneous nucleation. However, while the thermal conductivity is known to diverge at the vapor-liquid critical point due to critical density fluctuations, the thermal conductivity of supercooled water, calculated as the product of thermal diffusivity and heat capacity, does not show any sign of such an anomaly. We have used mode-coupling theory to investigate the possible effect of critical fluctuations on the thermal conductivity of supercooled water and found that indeed any critical thermal-conductivity enhancement would be too small to be measurable at experimentally accessible temperatures. Moreover, the behavior of thermal conductivity can be explained by the observed anomalies of the thermodynamic properties. In particular, we show that thermal conductivity should go through a minimum when temperature is decreased, as Kumar and Stanley observed in the TIP5P model of water. We discuss physical reasons for the striking difference between the behavior of thermal conductivity in water near the vapor-liquid and liquid-liquid critical points.

  12. Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

    Science.gov (United States)

    Tournier, Robert F.

    2018-01-01

    Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

  13. COOPERATIVITY, CAGE EFFECT AND HOPPING DIFFUSION IN SUPERCOOLED LIQUIDS AND GLASSES

    Directory of Open Access Journals (Sweden)

    A.S.Bakai

    2003-01-01

    Full Text Available Molecular dynamic simulations of structure, thermodynamic and kinetic properties of model metallic Ag-Cu alloy are performed to elucidate its behavior at glass transition. In spite of small variations of inherent structure of the alloy the relaxation kinetics undergo dramatic changes at the glass transition. The time dependences of the mean square displacements and the non-Gaussianity parameter show the signs of anomalous diffusion in an intermediate time region. The analysis of time evolution of van Hove correlation function indicates the existence of both jump displacements and short-range cooperative atomic rearrangements. Below Tg these cooperative rearrangements do not contribute to a long-range diffusion but they still dominate the relaxation at short time.

  14. Molecular Beam Studies of Reactions between Stratospheric Gases and Supercooled Sulfuric Acid

    National Research Council Canada - National Science Library

    Nathanson, Gilbert

    2000-01-01

    ..., which catalytically destroy ozone. The first step in these reactions is the transport of gas phase HCl and HBr molecules through the surface of the liquid aerosol and into the acid, where they dissolve and dissociate...

  15. Supercooled Liquid Water Content Instrument Analysis and Winter 2014 Data with Comparisons to the NASA Icing Remote Sensing System and Pilot Reports

    Science.gov (United States)

    King, Michael C.

    2016-01-01

    The National Aeronautics and Space Administration (NASA) has developed a system for remotely detecting the hazardous conditions leading to aircraft icing in flight, the NASA Icing Remote Sensing System (NIRSS). Newly developed, weather balloon-borne instruments have been used to obtain in-situ measurements of supercooled liquid water during March 2014 to validate the algorithms used in the NIRSS. A mathematical model and a processing method were developed to analyze the data obtained from the weather balloon soundings. The data from soundings obtained in March 2014 were analyzed and compared to the output from the NIRSS and pilot reports.

  16. Kinetics of crystal growth in amorphous solid and supercooled liquid TeSe20 using DTA and d.c. conductivity measurements

    International Nuclear Information System (INIS)

    Kotkata, M.F.; Mahmoud, E.A.; El-Mously, M.K.

    1979-07-01

    Curves of reaction rate versus temperature for constant heating rates (phi=1-10 0 C/min) constructed by analytical methods have been used to demonstrate the crystallization kinetics of amorphous solid TeSe 20 . The devitrification process takes place with predominance of random nucleation and one-dimensional growth, and is limited by combined switching and splitting of the chemical bonds. The mean value for the activation energy of the amorphous-crystal transformation, average E, is found to be 64 Kcal/mole. While, the quantity E calculated on the basis of d.c. conductivity changes during different isothermal crystallization (120-175 0 C) in supercooled liquid TeSe 20 , amounts to 11.5 Kcal/mole and suggests the existence of mixed chains in the liquid alloys. (author)

  17. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  18. Raman non-coincidence effect of boroxol ring: The interplay between repulsion and attraction forces in the glassy, supercooled and liquid state

    Science.gov (United States)

    Kalampounias, Angelos G.; Papatheodorou, George N.

    2018-06-01

    Temperature dependent Raman spectra of boric oxide have been measured in a temperature range covering the glassy, supercooled and liquid state. The shift of the isotropic band assigned to boroxol rings relative to the anisotropic component upon heating the glass is measured and attributed to the Raman non-coincidence effect. The measured shift is associated with the competition between attraction and repulsion forces with increasing temperature. The relation of dephasing and orientational relaxation times to the non-coincidence effect of the condensed phases has been examined. We discuss our results in the framework of the current phenomenological status of the field in an attempt to separate the attraction and repulsion contributions corresponding to the observed non-coincidence effect.

  19. Frequency and Wavevector Dependence of the Atomic Level Stress-Stress Correlation Function in a Model Supercooled Liquid

    Science.gov (United States)

    Levashov, Valentin A.; Morris, James R.; Egami, Takeshi

    2012-02-01

    Temporal and spatial correlations among the local atomic level shear stresses were studied for a model liquid iron by molecular dynamics simulation [PRL 106,115703]. Integration over time and space of the shear stress correlation function F(r,t) yields viscosity via Green-Kubo relation. The stress correlation function in time and space F(r,t) was Fourier transformed to study the dependence on frequency, E, and wave vector, Q. The results, F(Q,E), showed damped shear stress waves propagating in the liquid for small Q at high and low temperatures. We also observed additional diffuse feature that appears as temperature is reduced below crossover temperature of potential energy landscape at relatively low frequencies at small Q. We suggest that this additional feature might be related to dynamic heterogeneity and boson peaks. We also discuss a relation between the time-scale of the stress-stress correlation function and the alpha-relaxation time of the intermediate self-scattering function S(Q,E).

  20. Vapor-deposited non-crystalline phase vs ordinary glasses and supercooled liquids: Subtle thermodynamic and kinetic differences

    International Nuclear Information System (INIS)

    Bhattacharya, Deepanjan; Sadtchenko, Vlad

    2015-01-01

    Vapor deposition of molecules on a substrate often results in glassy materials of high kinetic stability and low enthalpy. The extraordinary properties of such glasses are attributed to high rates of surface diffusion during sample deposition, which makes it possible for constituents to find a configuration of much lower energy on a typical laboratory time scale. However, the exact nature of the resulting phase and the mechanism of its formation are not completely understood. Using fast scanning calorimetry technique, we show that out-of-equilibrium relaxation kinetics and possibly the enthalpy of vapor-deposited films of toluene and ethylbenzene, archetypical fragile glass formers, are distinct from those of ordinary supercooled phase even when the deposition takes place at temperatures above the ordinary glass softening transition temperatures. These observations along with the absolute enthalpy dependences on deposition temperatures support the conjecture that the vapor-deposition may result in formation of non-crystalline phase of unique structural, thermodynamic, and kinetic properties

  1. Molecular dynamics of liquid crystals

    Science.gov (United States)

    Sarman, Sten

    1997-02-01

    We derive Green-Kubo relations for the viscosities of a nematic liquid crystal. The derivation is based on the application of a Gaussian constraint algorithm that makes the director angular velocity of a liquid crystal a constant of motion. Setting this velocity equal to zero means that a director-based coordinate system becomes an inertial frame and that the constraint torques do not do any work on the system. The system consequently remains in equilibrium. However, one generates a different equilibrium ensemble. The great advantage of this ensemble is that the Green-Kubo relations for the viscosities become linear combinations of time correlation function integrals, whereas they are complicated rational functions in the conventional canonical ensemble. This facilitates the numerical evaluation of the viscosities by molecular dynamics simulations.

  2. Crystallization Behavior and Relaxation Dynamics of Supercooled S‑Ketoprofen and the Racemic Mixture along an Isochrone

    DEFF Research Database (Denmark)

    Adrjanowicz, Karolina; Kaminski, Kamil; Paluch, Marian

    2015-01-01

    In this paper, we study crystallization behavior and molecular dynamics in the supercooled liquid state of the pharmaceutically important compound ketoprofen at various thermodynamic conditions. Dielectric relaxation for a racemic mixture was investigated in a wide range of temperatures and press...

  3. Nano-viscosity of supercooled liquid measured by fluorescence correlation spectroscopy: Pressure and temperature dependence and the density scaling

    Science.gov (United States)

    Meier, G.; Gapinski, J.; Ratajczyk, M.; Lettinga, M. P.; Hirtz, K.; Banachowicz, E.; Patkowski, A.

    2018-03-01

    The Stokes-Einstein relation allows us to calculate apparent viscosity experienced by tracers in complex media on the basis of measured self-diffusion coefficients. Such defined nano-viscosity values can be obtained through single particle techniques, like fluorescence correlation spectroscopy (FCS) and particle tracking (PT). In order to perform such measurements, as functions of pressure and temperature, a new sample cell was designed and is described in this work. We show that this cell in combination with a long working distance objective of the confocal microscope can be used for successful FCS, PT, and confocal imaging experiments in broad pressure (0.1-100 MPa) and temperature ranges. The temperature and pressure dependent nano-viscosity of a van der Waals liquid obtained from the translational diffusion coefficient measured in this cell by means of FCS obeys the same scaling as the rotational relaxation and macro-viscosity of the system.

  4. Dielectric relaxation studies in super-cooled liquid and glassy phases of anti-cancerous alkaloid: Brucine

    Science.gov (United States)

    Afzal, Aboothahir; Shahin Thayyil, M.; Sulaiman, M. K.; Kulkarni, A. R.

    2018-05-01

    Brucine has good anti-tumor effects, on both liver cancer and breast cancer. It has bioavailability of 40.83%. Since the bioavailability of the drug is low, an alternative method to increase its bioavailability and solubility is by changing the drug into glassy form. We used Differential Scanning Calorimetry (DSC) for studying the glass forming ability of the drug. Brucine was found to be a very good glass former glass transition temperature 365 K. Based on the DSC analysis we have used broadband dielectric spectroscopy (BDS) for studying the drug in the super cooled and glassy state. BDS is an effective tool to probe the molecular dynamics in the super cooled and glassy state. Molecular mobility is found to be present even in the glassy state of this active pharmaceutical ingredient (API) which is responsible for the instability. Our aim is to study the factors responsible for instability of this API in amorphous form. Cooling curves for dielectric permittivity and dielectric loss revealed the presence of structural (α) and secondary relaxations (β and γ). Temperature dependence of relaxation time is fitted by Vogel-Fulcher-Tammann equation and found the values of activation energy of the α relaxation, fragility and glass transition temperature. Paluch's anti correlation is also verified, that the width of the α-loss peak at or near the glass transition temperature Tg is strongly anticorrelated with the polarity of the molecule. The larger the dielectric relaxation strength Δɛ (Tg) of the system, the narrower is the α-loss peak (higher value of βKWW).

  5. Evidence for the existence of supercooled ethane droplets under conditions prevalent in Titan's atmosphere.

    Science.gov (United States)

    Sigurbjörnsson, Omar F; Signorell, Ruth

    2008-11-07

    Recent evidence for ethane clouds and condensation in Titan's atmosphere raise the question whether liquid ethane condensation nuclei and supercooled liquid ethane droplets exist under the prevalent conditions. We present laboratory studies on the phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions relevant to Titan's atmosphere. Combining bath gas cooling with infrared spectroscopy, we find evidence for the existence of supercooled liquid ethane aerosol droplets. The observed homogeneous freezing rates imply that supercooled ethane could be a long-lived species in ethane-rich regions of Titan's atmosphere similar to supercooled water in the Earth's atmosphere.

  6. Solidity of viscous liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    1999-01-01

    Recent NMR experiments on supercooled toluene and glycerol by Hinze and Böhmer show that small rotation angles dominate with only a few large molecular rotations. These results are here interpreted by assuming that viscous liquids are solidlike on short length scales. A characteristic length...

  7. The Widom line of supercooled water

    International Nuclear Information System (INIS)

    Franzese, Giancarlo; Stanley, H Eugene

    2007-01-01

    Water can be supercooled to temperatures as low as -92 deg. C, the experimental crystal homogeneous nucleation temperature T H at 2 kbar. Within the supercooled liquid phase its response functions show an anomalous increase consistent with the presence of a liquid-liquid critical point located in a region inaccessible to experiments on bulk water. Recent experiments on the dynamics of confined water show that a possible way to understand the properties of water is to investigate the supercooled phase diagram in the vicinity of the Widom line (locus of maximum correlation length) that emanates from the hypothesized liquid-liquid critical point. Here we explore the Widom line for a Hamiltonian model of water using an analytic approach, and discuss the plausibility of the hypothesized liquid-liquid critical point, as well as its possible consequences, on the basis of the assumptions of the model. The present analysis allows us (i) to find an analytic expression for the spinodal line of the high-density liquid phase, with respect to the low-density liquid phase, showing that this line becomes flat in the P-T phase diagram in the physical limit of a large number of available orientations for the hydrogen bonds, as recently seen in simulations and experiments (Xu et al 2005 Proc. Natl Acad. Sci. 102 16558); (ii) to find an estimate of the values for the hypothesized liquid-liquid critical point coordinates that compare very well with Monte Carlo results; and (iii) to show how the Widom line can be located by studying the derivative of the probability of forming hydrogen bonds with local tetrahedral orientation which can be calculated analytically within this approach

  8. Mechanism of supercooled droplet freezing on surfaces.

    Science.gov (United States)

    Jung, Stefan; Tiwari, Manish K; Doan, N Vuong; Poulikakos, Dimos

    2012-01-10

    Understanding ice formation from supercooled water on surfaces is a problem of fundamental importance and general utility. Superhydrophobic surfaces promise to have remarkable 'icephobicity' and low ice adhesion. Here we show that their icephobicity can be rendered ineffective by simple changes in environmental conditions. Through experiments, nucleation theory and heat transfer physics, we establish that humidity and/or the flow of a surrounding gas can fundamentally switch the ice crystallization mechanism, drastically affecting surface icephobicity. Evaporative cooling of the supercooled liquid can engender ice crystallization by homogeneous nucleation at the droplet-free surface as opposed to the expected heterogeneous nucleation at the substrate. The related interplay between droplet roll-off and rapid crystallization is also studied. Overall, we bring a novel perspective to icing and icephobicity, unveiling the strong influence of environmental conditions in addition to the accepted effects of the surface conditions and hydrophobicity.

  9. Simulations of the flipping images and microparameters of molecular orientations in liquids according to the molecule string model

    International Nuclear Information System (INIS)

    Wang Li-Na; Zhao Xing-Yu; Zhang Li-Li; Huang Yi-Neng

    2012-01-01

    The relaxation dynamics of liquids is one of the fundamental problems in liquid physics, and it is also one of the key issues to understand the glass transition mechanism. It will undoubtedly provide enlightenment on understanding and calculating the relaxation dynamics if the molecular orientation flipping images and relevant microparameters of liquids are studied. In this paper, we first give five microparameters to describe the individual molecular string (MS) relaxation based on the dynamical Hamiltonian of the MS model, and then simulate the images of individual MS ensemble, and at the same time calculate the parameters of the equilibrium state. The results show that the main molecular orientation flipping image in liquids (including supercooled liquid) is similar to the random walk. In addition, two pairs of the parameters are equal, and one can be ignored compared with the other. This conclusion will effectively reduce the difficulties in calculating the individual MS relaxation based on the single-molecule orientation flipping rate of the general Glauber type, and the computer simulation time of interaction MS relaxation. Moreover, the conclusion is of reference significance for solving and simulating the multi-state MS model. (condensed matter: structural, mechanical, and thermal properties)

  10. Transport properties of supercooled confined water

    International Nuclear Information System (INIS)

    Mallamace, F.; Baglioni, P.; Corsaro, C.; Spooren, J.; Stanley, H.E.; Chen, S.-H.

    2011-01-01

    We present an overview of recent experiments performed on water in the deeply supercooled region, a temperature region of fundamental importance in the science of water. We examine data generated by nuclear magnetic resonance, quasi-elastic neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy, and study water confined in nanometer-scale environments. When contained within small pores, water does not crystallize and can be supercooled well below its homogeneous nucleation temperature T H. On this basis, it is possible to carry out a careful analysis of the well-known thermodynamic anomalies of water. Studying the temperature and pressure dependencies of water dynamics, we show that the liquid-liquid phase transition (LLPT) hypothesis represents a reliable model for describing liquid water. In this model, liquid water is a mixture of two different local structures: a low density liquid (LDL) and a high-density liquid (HDL). The LLPT line terminates at a low-T liquid-liquid critical point. We discuss the following experimental findings: 1.) the crossover from non-Arrhenius behavior at high T to Arrhenius behavior at low T in transport parameters; 2.) the breakdown of the Stokes-Einstein relation; 3.) the existence of a Widom line, which is the locus of points corresponding to a maximum correlation length in the P-T phase diagram and which ends in the liquid-liquid critical point; 4.) the direct observation of the LDL phase; and 5.) the minimum in the density at approximately 70 K below the temperature of the density maximum. In our opinion these results strongly support the LLPT hypothesis. All of the basic science and technology community should be impressed by the fact that, although the few ideas (apparently elementary) developed concerning water approximately 27 centuries ago have changed very little up to now, because of the current expansion in our knowledge in this area, they can begin to change in the near future.

  11. The interplay between dynamic heterogeneities and structure of bulk liquid water: A molecular dynamics simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Demontis, Pierfranco; Suffritti, Giuseppe B. [Dipartimento di Chimica e Farmacia, Università degli studi di Sassari, Sassari (Italy); Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Unità di ricerca di Sassari, Via Vienna, 2, I-07100 Sassari (Italy); Gulín-González, Jorge [Grupo de Matemática y Física Computacionales, Universidad de las Ciencias Informáticas (UCI), Carretera a San Antonio de los Baños, Km 21/2, La Lisa, La Habana (Cuba); Masia, Marco [Dipartimento di Chimica e Farmacia, Università degli studi di Sassari, Sassari (Italy); Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Unità di ricerca di Sassari, Via Vienna, 2, I-07100 Sassari (Italy); Istituto Officina dei Materiali del CNR, UOS SLACS, Via Vienna 2, 07100 Sassari (Italy); Sant, Marco [Dipartimento di Chimica e Farmacia, Università degli studi di Sassari, Sassari (Italy)

    2015-06-28

    In order to study the interplay between dynamical heterogeneities and structural properties of bulk liquid water in the temperature range 130–350 K, thus including the supercooled regime, we use the explicit trend of the distribution functions of some molecular properties, namely, the rotational relaxation constants, the atomic mean-square displacements, the relaxation of the cross correlation functions between the linear and squared displacements of H and O atoms of each molecule, the tetrahedral order parameter q and, finally, the number of nearest neighbors (NNs) and of hydrogen bonds (HBs) per molecule. Two different potentials are considered: TIP4P-Ew and a model developed in this laboratory for the study of nanoconfined water. The results are similar for the dynamical properties, but are markedly different for the structural characteristics. In particular, for temperatures higher than that of the dynamic crossover between “fragile” (at higher temperatures) and “strong” (at lower temperatures) liquid behaviors detected around 207 K, the rotational relaxation of supercooled water appears to be remarkably homogeneous. However, the structural parameters (number of NNs and of HBs, as well as q) do not show homogeneous distributions, and these distributions are different for the two water models. Another dynamic crossover between “fragile” (at lower temperatures) and “strong” (at higher temperatures) liquid behaviors, corresponding to the one found experimentally at T{sup ∗} ∼ 315 ± 5 K, was spotted at T{sup ∗} ∼ 283 K and T{sup ∗} ∼ 276 K for the TIP4P-Ew and the model developed in this laboratory, respectively. It was detected from the trend of Arrhenius plots of dynamic quantities and from the onset of a further heterogeneity in the rotational relaxation. To our best knowledge, it is the first time that this dynamical crossover is detected in computer simulations of bulk water. On the basis of the simulation results, the possible

  12. Supercooled smectic nanoparticles

    DEFF Research Database (Denmark)

    Kuntsche, Judith; Koch, Michel H J; Fahr, Alfred

    2009-01-01

    Cholesteryl nonanoate (CN), myristate (CM), palmitate (CP) and oleate (CO) alone or in combination were evaluated as matrix lipids for the preparation of supercooled smectic nanoparticles with a high stability against recrystallization during storage. The phase behavior of the cholesterol esters......, laser diffraction combined with polarizing intensity differential scattering, DSC and SAXS. The morphology of selected formulations was studied by freeze-fracture electron microscopy. All smectic nanoparticles with a mixed cholesterol ester matrix were stable against recrystallization when stored...... at room temperature. Nanoparticles with a pure CN and mixed CM/CN matrix with a high fraction of CN (60% of the whole lipid matrix) could even be stored at 4 degrees C for at least 18 months without any recrystallization. As smectic nanoparticles are studied especially with regard to parenteral...

  13. On the abundance and general nature of the liquid-liquid phase transition in molecular systems

    International Nuclear Information System (INIS)

    Kurita, Rei; Tanaka, Hajime

    2005-01-01

    Even a single-component liquid may have more than two kinds of isotropic liquid states. The transition between these different states is called a liquid-liquid transition (LLT). An LLT has been considered to be a rather rare phenomenon, in particular for molecular liquids. Very recently, however, we found an LLT in triphenyl phosphite, which may be the first experimental observation of an LLT for molecular liquids. Here we report convincing evidence of the second example of LLT for another molecular liquid, n-butanol. Despite large differences in the chemical structure and the molecular shape between triphenyl phosphite and n-butanol, the basic features of the transformation kinetics are strikingly similar. This suggests that an LLT may not be a rare phenomenon restricted to specific liquids, but may exist in various molecular liquids, which have a tendency to form long-lived locally favoured structures due to anisotropic interactions (e.g., hydrogen bonding). (letter to the editor)

  14. Comment on "Spontaneous liquid-liquid phase separation of water"

    Science.gov (United States)

    Limmer, David T.; Chandler, David

    2015-01-01

    Yagasaki et al. [Phys. Rev. E 89, 020301 (2014), 10.1103/PhysRevE.89.020301] present results from a molecular dynamics trajectory illustrating coarsening of ice, which they interpret as evidence of transient coexistence between two distinct supercooled phases of liquid water. We point out that neither two distinct liquids nor criticality are demonstrated in this simulation study. Instead, the illustrated trajectory is consistent with coarsening behaviors analyzed and predicted in earlier work by others.

  15. Comment on "Spontaneous liquid-liquid phase separation of water".

    Science.gov (United States)

    Limmer, David T; Chandler, David

    2015-01-01

    Yagasaki et al. [Phys. Rev. E 89, 020301 (2014)] present results from a molecular dynamics trajectory illustrating coarsening of ice, which they interpret as evidence of transient coexistence between two distinct supercooled phases of liquid water. We point out that neither two distinct liquids nor criticality are demonstrated in this simulation study. Instead, the illustrated trajectory is consistent with coarsening behaviors analyzed and predicted in earlier work by others.

  16. Liquid ammonia: Molecular correlation functions from x-ray diffraction

    International Nuclear Information System (INIS)

    Narten, A.H.

    1977-01-01

    For nearly spherical molecules the x-ray scattering from liquids yields structure and correlation functions for molecular centers. The distribution of electron density in an ammonia molecular is very nearly spherical, and orientational correlation between molecules in the liquid is not ''seen'' by x rays. Structure and correlation functions for molecular centers (nitrogen atoms) are derived from x-ray data on liquid NH 3 at 4 degreeC and tabulated. They provide a sensitive test for future work on a molecular theory of liquid ammonia

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

    Science.gov (United States)

    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.

  18. Molecular dynamics beyonds the limits: Massive scaling on 72 racks of a BlueGene/P and supercooled glass dynamics of a 1 billion particles system

    KAUST Repository

    Allsopp, Nicholas

    2012-04-01

    We report scaling results on the world\\'s largest supercomputer of our recently developed Billions-Body Molecular Dynamics (BBMD) package, which was especially designed for massively parallel simulations of the short-range atomic dynamics in structural glasses and amorphous materials. The code was able to scale up to 72 racks of an IBM BlueGene/P, with a measured 89% efficiency for a system with 100 billion particles. The code speed, with 0.13. s per iteration in the case of 1 billion particles, paves the way to the study of billion-body structural glasses with a resolution increase of two orders of magnitude with respect to the largest simulation ever reported. We demonstrate the effectiveness of our code by studying the liquid-glass transition of an exceptionally large system made by a binary mixture of 1 billion particles. © 2012.

  19. METHANE GAS STABILIZES SUPERCOOLED ETHANE DROPLETS IN TITAN'S CLOUDS

    International Nuclear Information System (INIS)

    Wang, Chia C.; Lang, E. Kathrin; Signorell, Ruth

    2010-01-01

    Strong evidence for ethane clouds in various regions of Titan's atmosphere has recently been found. Ethane is usually assumed to exist as ice particles in these clouds, although the possible role of liquid and supercooled liquid ethane droplets has been recognized. Here, we report on infrared spectroscopic measurements of ethane aerosols performed in the laboratory under conditions mimicking Titan's lower atmosphere. The results clearly show that liquid ethane droplets are significantly stabilized by methane gas which is ubiquitous in Titan's nitrogen atmosphere-a phenomenon that does not have a counterpart for water droplets in Earth's atmosphere. Our data imply that supercooled ethane droplets are much more abundant in Titan's clouds than previously anticipated. Possibly, these liquid droplets are even more important for cloud processes and the formation of lakes than ethane ice particles.

  20. Experimental evidence for two distinct deeply supercooled liquid states of water – Response to “Comment on ‘Water's second glass transition”’, by G.P. Johari, Thermochim. Acta (2015)

    Energy Technology Data Exchange (ETDEWEB)

    Stern, J.; Seidl, M. [Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck (Austria); Gainaru, C. [Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund (Germany); Fuentes-Landete, V.; Amann-Winkel, K.; Handle, P.H. [Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck (Austria); Köster, K.W.; Nelson, H. [Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund (Germany); Böhmer, R., E-mail: roland.bohmer@tu-dortmund.de [Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund (Germany); Loerting, T., E-mail: thomas.loerting@uibk.ac.at [Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck (Austria)

    2015-10-10

    Highlights: • Two samples of amorphous ices quench-recovered from 140 K to 0.07 GPa are compared. • Calorimetry, X-ray diffraction, dielectric spectroscopy and volumetry are employed. • The two samples are distinct and cannot both be termed “pressure-densified glassy water”. • One route of preparation leads to high- (HDA), and the other to low-density amorphous ice (LDA). • Two distinct glass transitions are observed and interpreted to indicate two liquid H{sub 2}O phases. - Abstract: Recently, our earlier data which led us to conclude that deeply supercooled water displays a second glass transition (Amann-Winkel et al., 2013) was reinterpreted (Johari, 2015). In particular, the increase in heat capacity observed for high-density amorphous ice (HDA) samples at 116 K was reinterpreted to indicate sub-T{sub g} features of low-density amorphous ice's (LDA's) glass transition. We reply to the criticism in detail and report an experiment triggered by the comment on our work. This experiment unequivocally confirms our original interpretation of the observations and reinforces the case for water's second glass transition, its polyamorphism, and the observation of two distinct ultraviscous states of water differing by about 25% in density.

  1. Supercooling of natural water, heavy water and of the blends H2O-D2O

    International Nuclear Information System (INIS)

    Lafargue, C.; Babin, L.; Clausse, D.; Lere-Porte, M.; Broto, F.

    1975-01-01

    It is shown that the coherency of the results of various measurements on water freezing temperatures proves that freezing temperatures must be dependent on the structure of the supercooled liquid. Recent experiments that confirm this interpretation are described: study of the stability of supercooled water as a function of time at fixed temperature, study of the influence of various thermal treatments on the behavior of supercooled water, study of the supercooling of heavy water and of D 2 O-H 2 O blends [fr

  2. Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirin

    International Nuclear Information System (INIS)

    Zhang Yang; Mamontov, Eugene; Tyagi, Madhusudan; Chen, Sow-Hsin

    2012-01-01

    Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent β(Q) is independent of the wavevector transfer Q in the measured Q range and (ii) the structural relaxation time τ(Q) follows a power-law dependence on Q. Consequently, the Q-independent structural relaxation time τ 0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of τ 0 can be fitted with the mode-coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by Tokuyama in the measured temperature range. The calculated dynamic response function χ T (Q, t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement (x 2 ) and the non-Gaussian parameter α 2 extracted from the elastic scattering.

  3. Quasi-Elastic Neutron Scattering Studies of the Slow Dynamics of Supercooled and Glassy Aspirin

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yang [ORNL; Tyagi, M. [NCNR and University of Maryland; Mamontov, Eugene [ORNL; Chen, Sow-hsin H [ORNL

    2011-01-01

    Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 K down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent (Q) is independent of the wave vector transfer Q in the measured Q-range, and (ii) the structural relaxation time (Q) follows a power law dependence on Q. Consequently, the Q-independent structural relaxation time 0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of 0 can be fitted with the mode coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by M. Tokuyama in the measured temperature range. The calculated dynamic response function T(Q,t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows a direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement x2 and non-Gaussian parameter 2 extracted from the elastic scattering.

  4. Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirin

    Science.gov (United States)

    Zhang, Yang; Tyagi, Madhusudan; Mamontov, Eugene; Chen, Sow-Hsin

    2012-02-01

    Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent β(Q) is independent of the wavevector transfer Q in the measured Q range and (ii) the structural relaxation time τ(Q) follows a power-law dependence on Q. Consequently, the Q-independent structural relaxation time τ0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of τ0 can be fitted with the mode-coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by Tokuyama in the measured temperature range. The calculated dynamic response function χT(Q, t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement langx2rang and the non-Gaussian parameter α2 extracted from the elastic scattering.

  5. Molecular simulation of ionic liquids: current status and future opportunities

    International Nuclear Information System (INIS)

    Maginn, E J

    2009-01-01

    Ionic liquids are salts that are liquid near ambient conditions. Interest in these unusual compounds has exploded in the last decade, both at the academic and commercial level. Molecular simulations based on classical potentials have played an important role in helping researchers understand how condensed phase properties of these materials are linked to chemical structure and composition. Simulations have also predicted many properties and unexpected phenomena that have subsequently been confirmed experimentally. The beneficial impact molecular simulations have had on this field is due in large part to excellent timing. Just when computing power and simulation methods matured to the point where complex fluids could be studied in great detail, a new class of materials virtually unknown to experimentalists came on the scene and demanded attention. This topical review explores some of the history of ionic liquid molecular simulations, and then gives examples of the recent use of molecular dynamics and Monte Carlo simulation in understanding the structure of ionic liquids, the sorption of small molecules in ionic liquids, the nature of ionic liquids in the vapor phase and the dynamics of ionic liquids. This review concludes with a discussion of some of the outstanding problems facing the ionic liquid modeling community and how condensed phase molecular simulation experts not presently working on ionic liquids might help advance the field. (topical review)

  6. Elastic properties of surfactant monolayers at liquid-liquid interfaces: A molecular dynamics study

    DEFF Research Database (Denmark)

    Laradji, Mohamed; Mouritsen, Ole G.

    2000-01-01

    Using a simple molecular model based on the Lennard-Jones potential, we systematically study the elastic properties of liquid-liquid interfaces containing surfactant molecules by means of extensive and large-scale molecular dynamics simulations. The main elastic constants of the interface, corres...

  7. Nonlinear permittivity spectra of supercooled ionic liquids: Observation of a "hump" in the third-order permittivity spectra and comparison to double-well potential models.

    Science.gov (United States)

    Patro, L N; Burghaus, O; Roling, B

    2017-04-21

    We have measured the third-order permittivity spectra ε 3 3 of a monocationic and of a dicationic liquid close to the glass transition temperature by applying ac electric fields with large amplitudes up to 180 kV/cm. A peak ("hump") in the modulus of ε 3 3 is observed for a mono-cationic liquid after subtraction of the dc contribution from the imaginary part of ε 3 3 . We show that the origin of this experimental "hump" is a peak in the imaginary part of ε 3 3 , with the peak height strongly increasing with decreasing temperature. Overall, the spectral shape of the third-order permittivity of both ionic liquids is similar to the predictions of a symmetric double well potential model, although this model does not predict a "hump" in the modulus. In contrast, an asymmetric double well potential model predicts a "hump," but the spectral shape of both the real and imaginary part of ε 3 3 deviates significantly from the experimental spectra. These results show that not only the modulus of ε 3 3 but also its phase is an important quantity when comparing experimental results with theoretical predictions.

  8. Singularity-free interpretation of the thermodynamics of supercooled water

    International Nuclear Information System (INIS)

    Sastry, S.; Debenedetti, P.G.; Sciortino, F.; Stanley, H.E.

    1996-01-01

    The pronounced increases in isothermal compressibility, isobaric heat capacity, and in the magnitude of the thermal expansion coefficient of liquid water upon supercooling have been interpreted either in terms of a continuous, retracing spinodal curve bounding the superheated, stretched, and supercooled states of liquid water, or in terms of a metastable, low-temperature critical point. Common to these two scenarios is the existence of singularities associated with diverging density fluctuations at low temperature. We show that the increase in compressibility upon lowering the temperature of a liquid that expands on cooling, like water, is not contingent on any singular behavior, but rather is a thermodynamic necessity. We perform a thermodynamic analysis for an anomalous liquid (i.e., one that expands when cooled) in the absence of a retracing spinodal and show that one may in general expect a locus of compressibility extrema in the anomalous regime. Our analysis suggests that the simplest interpretation of the behavior of supercooled water consistent with experimental observations is free of singularities. We then develop a waterlike lattice model that exhibits no singular behavior, while capturing qualitative aspects of the thermodynamics of water. copyright 1996 The American Physical Society

  9. Control of liquid crystal molecular orientation using ultrasound vibration

    Energy Technology Data Exchange (ETDEWEB)

    Taniguchi, Satoki [Faculty of Life and Medical Sciences, Doshisha University, 1-3 Tataramiyakodani, Kyotanabe, Kyoto 610-0321 (Japan); Wave Electronics Research Center, Doshisha University, 1-3 Tataramiyakodani, Kyotanabe, Kyoto 610-0321 (Japan); Koyama, Daisuke; Matsukawa, Mami [Wave Electronics Research Center, Doshisha University, 1-3 Tataramiyakodani, Kyotanabe, Kyoto 610-0321 (Japan); Faculty of Science and Engineering, Doshisha University, 1-3 Tataramiyakodani, Kyotanabe, Kyoto 610-0321 (Japan); Shimizu, Yuki; Emoto, Akira [Faculty of Science and Engineering, Doshisha University, 1-3 Tataramiyakodani, Kyotanabe, Kyoto 610-0321 (Japan); Nakamura, Kentaro [Precision and Intelligence Laboratory, Tokyo Institute of Technology, 4259-R2-26, Nagatsuta-cho, Midori-ku, Yokohama 226-8503 (Japan)

    2016-03-07

    We propose a technique to control the orientation of nematic liquid crystals using ultrasound and investigate the optical characteristics of the oriented samples. An ultrasonic liquid crystal cell with a thickness of 5–25 μm and two ultrasonic lead zirconate titanate transducers was fabricated. By exciting the ultrasonic transducers, the flexural vibration modes were generated on the cell. An acoustic radiation force to the liquid crystal layer was generated, changing the molecular orientation and thus the light transmission. By modulating the ultrasonic driving frequency and voltage, the spatial distribution of the molecular orientation of the liquid crystals could be controlled. The distribution of the transmitted light intensity depends on the thickness of the liquid crystal layer because the acoustic field in the liquid crystal layer is changed by the orientational film.

  10. Near-wall molecular ordering of dilute ionic liquids

    NARCIS (Netherlands)

    Jitvisate, Monchai; Seddon, James Richard Thorley

    2017-01-01

    The interfacial behavior of ionic liquids promises tunable lubrication as well as playing an integral role in ion diffusion for electron transfer. Diluting the ionic liquids optimizes bulk parameters, such as electric conductivity, and one would expect dilution to disrupt the near-wall molecular

  11. Diffusion in Liquids : Equilibrium Molecular Simulations and Predictive Engineering Models

    NARCIS (Netherlands)

    Liu, X.

    2013-01-01

    The aim of this thesis is to study multicomponent diffusion in liquids using Molecular Dynamics (MD) simulations. Diffusion plays an important role in mass transport processes. In binary systems, mass transfer processes have been studied extensively using both experiments and molecular simulations.

  12. Are Ionic Liquids Good Boundary Lubricants? A Molecular Perspective

    Directory of Open Access Journals (Sweden)

    Romain Lhermerout

    2018-01-01

    Full Text Available The application of ionic liquids as lubricants has attracted substantial interest over the past decade and this has produced a rich literature. The aim of this review is to summarize the main findings about frictional behavior of ionic liquids in the boundary lubrication regime. We first recall why the unusual properties of ionic liquids make them very promising lubricants, and the molecular mechanisms at the origin of their lubricating behavior. We then point out the main challenges to be overcome in order to optimise ionic liquid lubricant performance for common applications. We finally discuss their use in the context of electroactive lubrication.

  13. Supercooling of aqueous NaCl and KCl solutions under acoustic levitation.

    Science.gov (United States)

    Lü, Y J; Wei, B

    2006-10-14

    The supercooling capability of aqueous NaCl and KCl solutions is investigated at containerless state by using acoustic levitation method. The supercooling of water is obviously enhanced by the alkali metal ions and increases linearly with the augmentation of concentrations. Furthermore, the supercooling depends on the nature of ions and is 2-3 K larger for NaCl solution than that for KCl solution in the present concentration range: Molecular dynamics simulations are performed to reveal the intrinsic correlation between supercoolability and microstructure. The translational and orientational order parameters are applied to quantitatively demonstrate the effect of ionic concentration on the hydrogen-bond network and ice melting point. The disrupted hydrogen-bond structure determines essentially the concentration dependence of supercooling. On the other hand, the introduced acoustic pressure suppresses the increase of supercooling by promoting the growth and coalescence of microbubbles, the effective nucleation catalysts, in water. However, the dissolved ions can weaken this effect, and moreover the degree varies with the ion type. This results in the different supercoolability for NaCl and KCl solutions under the acoustic levitation conditions.

  14. Molecular dynamics beyonds the limits: Massive scaling on 72 racks of a BlueGene/P and supercooled glass dynamics of a 1 billion particles system

    KAUST Repository

    Allsopp, Nicholas; Ruocco, Giancarlo; Fratalocchi, Andrea

    2012-01-01

    We report scaling results on the world's largest supercomputer of our recently developed Billions-Body Molecular Dynamics (BBMD) package, which was especially designed for massively parallel simulations of the short-range atomic dynamics

  15. Production of nanostructured molecular liquids by supercritical CO2 processing

    Directory of Open Access Journals (Sweden)

    Sudhir Kumar Sharma

    2017-01-01

    Full Text Available Stable molecular clusters of ibuprofen and naproxen were prepared in dry ice, by supersonic jet expansion of their supercritical CO2 drug formulations into a liquid nitrogen cooled collection vessel, with up to 80% yield. Mixing the “dry ice” in water, resulted in the solubilization of the clusters and in the case of ibuprofen, we were able to create solutions, with concentrations of up to 6 mg/ml, a 300-fold increase over previously reported values. Drop casting and ambient drying of these solutions on silicon substrate resulted in a stable, viscous liquid film, referred to as nanostructured molecular liquids. These liquids exhibited a highly aligned, fine (self-assembled super lattice features. In vitro cancer cell viability studies of these formulations exhibited similar cytotoxicity to that of the original raw materials, thus retaining their original potency. Besides its scientific importance, this invention is expected to open up new drug delivery platforms.

  16. Liquid -to-glass transition in bulk glass-forming Cu55-xZr45Agx alloys using molecular dynamic simulations

    Directory of Open Access Journals (Sweden)

    Celtek M.

    2011-05-01

    Full Text Available We report results from molecular dynamics (MD studies concerning the microscopic structure of the ternary, bulk metallic glass-forming Cu55-x Zr45Agx (x=0,10,20 alloys using tight-binding potentials. Understanding of the nature of Glass Forming Ability (GFA of studied alloys, GFA parameters, glass transition temperature (T-g, melting temperature (T-m, reduced glass transition temperature (T-g/T-m, the supercooled liquid region and other parameters were simulated and compared with experiments. The computed pair distribution functions reproduce well experimental x-ray data of Inoue and co-workers. Structure analysis of the Cu-Zr-Ag alloy based on MD simulation will be also presented

  17. Communication: Minimum in the thermal conductivity of supercooled water: A computer simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Bresme, F., E-mail: f.bresme@imperial.ac.uk [Chemical Physics Section, Department of Chemistry, Imperial College, London SW7 2AZ, United Kingdom and Department of Chemistry, Norwegian University of Science and Technology, Trondheim 7491 (Norway); Biddle, J. W.; Sengers, J. V.; Anisimov, M. A. [Institute for Physical Science and Technology, and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

    2014-04-28

    We report the results of a computer simulation study of the thermodynamic properties and the thermal conductivity of supercooled water as a function of pressure and temperature using the TIP4P-2005 water model. The thermodynamic properties can be represented by a two-structure equation of state consistent with the presence of a liquid-liquid critical point in the supercooled region. Our simulations confirm the presence of a minimum in the thermal conductivity, not only at atmospheric pressure, as previously found for the TIP5P water model, but also at elevated pressures. This anomalous behavior of the thermal conductivity of supercooled water appears to be related to the maximum of the isothermal compressibility or the minimum of the speed of sound. However, the magnitudes of the simulated thermal conductivities are sensitive to the water model adopted and appear to be significantly larger than the experimental thermal conductivities of real water at low temperatures.

  18. Communication: Minimum in the thermal conductivity of supercooled water: A computer simulation study

    International Nuclear Information System (INIS)

    Bresme, F.; Biddle, J. W.; Sengers, J. V.; Anisimov, M. A.

    2014-01-01

    We report the results of a computer simulation study of the thermodynamic properties and the thermal conductivity of supercooled water as a function of pressure and temperature using the TIP4P-2005 water model. The thermodynamic properties can be represented by a two-structure equation of state consistent with the presence of a liquid-liquid critical point in the supercooled region. Our simulations confirm the presence of a minimum in the thermal conductivity, not only at atmospheric pressure, as previously found for the TIP5P water model, but also at elevated pressures. This anomalous behavior of the thermal conductivity of supercooled water appears to be related to the maximum of the isothermal compressibility or the minimum of the speed of sound. However, the magnitudes of the simulated thermal conductivities are sensitive to the water model adopted and appear to be significantly larger than the experimental thermal conductivities of real water at low temperatures

  19. Molecular hydrodynamic approach to dynamical correlations in quantum liquids

    International Nuclear Information System (INIS)

    Rabani, Eran; Reichman, David R.

    2002-01-01

    A quantum molecular hydrodynamic formalism is developed for the study of dynamics in quantum liquids. The method combines exact static input, generated by path-integral Monte Carlo, and an approximate form of the quantum memory function for the solution of the exact quantum generalized Langevin equation under consideration. This methodology is applied to the study of the spectrum of density fluctuations in liquid para-H 2 . Using a physically motivated approximation for the memory function, semiquantitative agreement is obtained for S(k,ω) in comparison to the recent experiments of Bermejo et al. [Phys. Rev. Lett. 84, 5359 (2000)]. Improvement of the methodology and future applications are discussed

  20. NMR and molecular dynamics of small solutes in liquid crystals

    International Nuclear Information System (INIS)

    Luyten, P.R.

    1984-01-01

    NMR relaxation measurements, using a wide variety of modern pulse techniques, can yield valuable information about molecular motions. In this thesis the applicability of theories developed to describe spin relaxation phenomena in partially ordered media is studied for small solutes in liquid crystals. 1 H, 2 H, 13 C and 14 N relaxation measurements are interpreted by means of a model, in which fast anisotropic re-orientational motion in an orienting potential combined with contributions from cooperative fluctuations in the surrounding liquid crystal molecules, induce the observed frequency dependent relaxation behavior. (orig.)

  1. Molecular dynamics simulations of liquid crystals at interfaces

    International Nuclear Information System (INIS)

    Shield, Mark

    2002-01-01

    Molecular dynamics simulations of an atomistic model of 4-n-octyl-4'-cyanobiphenyl (8CB) were performed for thin films of 8CB on solid substrates (a pseudopotential representation of the molecular topography of the (100) crystal surface of polyethylene (PE), a highly ordered atomistic model of a pseudo-crystalline PE surface and an atomistic model of a partially orientated film of PE), free standing thin films of 8CB and 8CB droplets in a hexagonal pit. The systems showed strong homeotropic anchoring at the free volume interface and planar anchoring at the solid interface whose strength was dependent upon the surface present. The free volume interface also demonstrated weak signs of smectic wetting of the bulk. Simulations of thin free standing films of liquid crystals showed the ordered nature of the liquid crystals at the two free volume interfaces can be adopted by the region of liquid crystal molecules between the homeotropic layer at each interface only if there is a certain number of liquid crystal molecules present. The perpendicular anchoring imposed by the free volume interface and the solid interface for the thin films on the solid substrates resulted in some evidence for the liquid crystal director undergoing a continual rotation at low temperatures and a definite discontinuous change at higher temperatures. The liquid crystal alignment imparted by these substrates was found to depend upon the topography of the surface and not the direction of the polymer chains in the substrate. The liquid crystal was found to order via an epitaxy-like mechanism. The perpendicular anchoring results in a drop in the order - disorder transition temperature for the molecules in the region between the homeotropic layer at the free volume interface and the planar layers at the solid interface. An increase in the size of this region does not alter the transition temperature. The shape of the liquid crystal molecules is dependent upon the degree of order and thus the nematic

  2. Amorphization of Molecular Liquids of Pharmaceutical Drugs by Acoustic Levitation

    Directory of Open Access Journals (Sweden)

    C. J. Benmore

    2011-08-01

    Full Text Available It is demonstrated that acoustic levitation is able to produce amorphous forms from a variety of organic molecular compounds with different glass forming abilities. This can lead to enhanced solubility for pharmaceutical applications. High-energy x-ray experiments show that several viscous gels form from saturated pharmaceutical drug solutions after 10–20 min of levitation at room temperature, most of which can be frozen in solid form. Laser heating of ultrasonically levitated drugs can also result in the vitrification of molecular liquids, which is not attainable using conventional amorphization methods.

  3. Physical limit of stability in supercooled D2O and D2O+H2O mixtures

    Science.gov (United States)

    Kiselev, S. B.; Ely, J. F.

    2003-01-01

    The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O+H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water-high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull's expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS, which lies below the homogeneous nucleation temperature, TH. We show that CP2 always lies inside in the so-called "nonthermodynamic habitat" and physically does not exist. However, the concept of a second "virtual" critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O+H2O mixtures. As an example, we consider here an equimolar D2O+H2O mixture in normal and supercooled states at atmospheric pressure, P=0.1 MPa.

  4. Immobilization of molecular catalysts in supported ionic liquid phases.

    Science.gov (United States)

    Van Doorslaer, Charlie; Wahlen, Joos; Mertens, Pascal; Binnemans, Koen; De Vos, Dirk

    2010-09-28

    In a supported ionic liquid phase (SILP) catalyst system, an ionic liquid (IL) film is immobilized on a high-surface area porous solid and a homogeneous catalyst is dissolved in this supported IL layer, thereby combining the attractive features of homogeneous catalysts with the benefits of heterogeneous catalysts. In this review reliable strategies for the immobilization of molecular catalysts in SILPs are surveyed. In the first part, general aspects concerning the application of SILP catalysts are presented, focusing on the type of catalyst, support, ionic liquid and reaction conditions. Secondly, organic reactions in which SILP technology is applied to improve the performance of homogeneous transition-metal catalysts are presented: hydroformylation, metathesis reactions, carbonylation, hydrogenation, hydroamination, coupling reactions and asymmetric reactions.

  5. Structure of a molecular liquid GeI4

    International Nuclear Information System (INIS)

    Fuchizaki, Kazuhiro; Sakagami, Takahiro; Kohara, Shinji; Mizuno, Akitoshi; Asano, Yuta; Hamaya, Nozomu

    2016-01-01

    A molecular liquid GeI 4 is a candidate that undergoes a pressure-induced liquid-to-liquid phase transition. This study establishes the reference structure of the low-pressure liquid phase. Synchrotron x-ray diffraction measurements were carried out at several temperatures between the melting and the boiling points under ambient pressure. The molecule has regular tetrahedral symmetry, and the intramolecular Ge–I length of 2.51 Å is almost temperature-independent within the measured range. A reverse Monte Carlo (RMC) analysis is employed to find that the distribution of molecular centers remains self-similar against heating, and thus justifying the length-scaling method adopted in determining the density. The RMC analysis also reveals that the vertex-to-face orientation of the nearest molecules are not straightly aligned, but are inclined at about 20 degrees, thereby making the closest intermolecular I–I distance definitely shorter than the intramolecular one. The prepeak observed at  ∼1 Å −1 in the structural factor slightly shifts and increases in height with increasing temperature. The origin of the prepeak is clearly identified to be traces of the 111 diffraction peak in the crystalline state. The prepeak, assuming the residual spatial correlation between germanium sites in the densest direction, thus shifts toward lower wavenumbers with thermal expansion. The aspect that a relative reduction in molecular size associated with the volume expansion is responsible for the increase in the prepeak’s height is confirmed by a simulation, in which the molecular size is changed. (paper)

  6. Jet supercooling and molecular jet spectroscopy

    International Nuclear Information System (INIS)

    Wharton, L.; Levy, D.

    1979-01-01

    The marriage of the laser and the seeded supersonic jet has generated a family of new optical spectroscopic results. We shall discuss the essential features of the technique and some results. The results will include structural and dynamical views of NO 2 , NaAr, and I 2 -noble gas complexes. The extension of the method to heavier systems is illustrated with free base phthalocyanine

  7. Dynamic signature of molecular association in methanol

    International Nuclear Information System (INIS)

    Bertrand, C. E.; Copley, J. R. D.; Faraone, A.; Self, J. L.

    2016-01-01

    Quasielastic neutron scattering measurements and molecular dynamics simulations were combined to investigate the collective dynamics of deuterated methanol, CD 3 OD. In the experimentally determined dynamic structure factor, a slow, non-Fickian mode was observed in addition to the standard density-fluctuation heat mode. The simulation results indicate that the slow dynamical process originates from the hydrogen bonding of methanol molecules. The qualitative behavior of this mode is similar to the previously observed α-relaxation in supercooled water [M. C. Bellissent-Funel et al., Phys. Rev. Lett. 85, 3644 (2000)] which also originates from the formation and dissolution of hydrogen-bonded associates (supramolecular clusters). In methanol, however, this mode is distinguishable well above the freezing transition. This finding indicates that an emergent slow mode is not unique to supercooled water, but may instead be a general feature of hydrogen-bonding liquids and associating molecular liquids.

  8. Strain-induced friction anisotropy between graphene and molecular liquids

    Science.gov (United States)

    Liao, Meng; To, Quy-Dong; Léonard, Céline; Monchiet, Vincent; Vo, Van-Hoang

    2017-01-01

    In this paper, we study the friction behavior of molecular liquids with anisotropically strained graphene. Due to the changes of lattice and the potential energy surface, the friction is orientation dependent and can be computed by tensorial Green-Kubo formula. Simple quantitative estimations are also proposed for the zero-time response and agree reasonably well with the molecular dynamics results. From simulations, we can obtain the information of structures, dynamics of the system, and study the influence of strain and molecular shapes on the anisotropy degree. It is found that unilateral strain can increase friction in all directions but the strain direction is privileged. Numerical evidences also show that nonspherical molecules are more sensitive to strain and give rise to more pronounced anisotropy effects.

  9. Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water

    International Nuclear Information System (INIS)

    Singh, Rakesh S.; Bagchi, Biman

    2014-01-01

    The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) liquid phases in supercooled state. The explanations of thermodynamic and dynamic anomalies of supercooled water often invoke the possible influence of a liquid-liquid transition between two metastable liquid phases. To investigate both the role of thermodynamic anomalies and presence of distinct metastable liquid phases in supercooled water on ice nucleation, we employ density functional theoretical approach to find nucleation free energy barrier in different regions of phase diagram. The theory makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of free energy barrier on temperature near liquid-liquid critical point. These predictions can be tested by computer simulations as well as by controlled experiments

  10. Thermodynamics of Supercooled and Glassy Water

    Science.gov (United States)

    Debenedetti, Pablo G.

    1998-03-01

    The behavior of metastable water at low temperatures is unusual. The isothermal compressibility, the isobaric heat capacity, and the magnitude of the thermal expansion coefficient increase sharply upon supercooling, and structural relaxation becomes extremely sluggish at temperatures far above the glass transition(Angell, C.A., Annu. Rev. Phys. Chem., 34, 593, 1983)(Debenedetti, P.G., Metastable Liquids. Concepts and Principles, Princeton University Press, 1996). Water has two distinct glassy phases, low- and high-density amorphous ice (LDA, HDA). The transition between LDA and HDA is accompanied by sharp volume and enthalpy changes, and appears to be first-order(Mishima, O., L.D.Calvert, and E. Whalley, Nature, 314, 76, 1985)(Mishima, O., J. Chem. Phys., 100, 5910, 1994). The understanding of these observations in terms of an underlying global phase behavior remains incomplete(Speedy, R.J., J. Phys. Chem., 86, 982, 1982)(Poole, P.H., F. Sciortino, U. Essman, and H.E. Stanley, Nature, 360, 324, 1992)(Sastry, S., P.G. Debenedetti, F. Sciortino, and H.E. Stanley, Phys. Rev. E, 53, 6144, 1996)(Tanaka, H., Nature, 380, 328, 1996)(Xie, Y., K.F. Ludwig, G. Morales, D.E. Hare, and C.M. Sorensen, Phys. Rev. Lett., 71, 2050, 1993). Microscopic theories and computer simulations suggest several scenarios that can reproduce some experimental observations. Interesting and novel ideas have resulted from this body of theoretical work, such as the possibility of liquid-liquid immiscibility in a pure substance(Poole, P.H., F.Sciortino, T.Grande, H.E. Stanley, and C.A. Angell, Phys. Rev. Lett., 73, 1632, 1994)(Roberts, C.J., and P.G. Debenedetti, J. Chem. Phys., 105, 658, 1996)(Roberts, C.J., P.G. Debenedetti, and A.Z. Panagiotopoulos, Phys. Rev. Lett., 77, 4386, 1996)(Harrington, S., R. Zhang, P.H. Poole, F. Sciortino, and H.E. Stanley, Phys. Rev. Lett., 78, 2409, 1997). In this talk I will review the experimental facts, discuss their theoretical interpretation, and identify key

  11. Forecasting of heat capacity of molecular inorganic liquids

    International Nuclear Information System (INIS)

    Sladkov, I.B.; Neganov, O.S.

    1992-01-01

    On the basis of analysis of experimental material on heat capacity of liquids, covering 350 molecular inorganic compounds, atomic parts of heat capacity for 58 elements of the Periodic system were obtained. Data on the accuracy of heat capacity calculation by the Neumann-Kopp rule using the recommended atomic parts C p are presented. For the Kelli rule it is assertained that the factor of proportiomality between heat capacity and the number of atoms in compound molecule in the general case depends on the type of anion and compound coordination. The Neumann-Kopp-Kelli rules provide a satisfactory accuracy of prediction

  12. Surface Tension of Supercooled Water Determined by Using a Counterpressure Capillary Rise Method

    Czech Academy of Sciences Publication Activity Database

    Vinš, Václav; Fransen, M. A. L. J.; Hykl, Jiří; Hrubý, Jan

    2015-01-01

    Roč. 119, č. 17 (2015), s. 5567-5575 ISSN 1520-6106 R&D Projects: GA MŠk LG13056; GA ČR GJ15-07129Y Institutional support: RVO:61388998 Keywords : capillary tube * interfacial tension * metastable liquid * supercooled liquid Subject RIV: BJ - Thermodynamics Impact factor: 3.187, year: 2015 http://pubs.acs.org/doi/abs/10.1021/acs.jpcb.5b00545

  13. Nonresonant Multiple-Pulse Control of Molecular Motions in Liquid

    Directory of Open Access Journals (Sweden)

    Nikiforov V.G.

    2015-01-01

    Full Text Available We propose the implementation of the multiple-pulse excitation for manipulation of the molecular contributions to the optically-heterodyne-detected optical-Kerr-effect. The key parameters controlling the specificity of the multiple-pulse excitation scenarios are the pulses durations, the delays between pulses, the relation between the pump pulses amplitudes and the pulses polarizations. We model the high-order optical responses and consider some principles of the scenarios construction. We show that it is possible to adjust the excitation scenario in such a way that the some responses can be removed from detected signal along with the enhancement of the interested response amplitude. The theoretical analysis and first experimental data reveal that the multiple-pulse excitation technique can be useful for the selective spectroscopy of the molecular vibrations and rotations in liquid.

  14. Rheology of liquid n-triacontane: Molecular dynamics simulation

    International Nuclear Information System (INIS)

    Kondratyuk, N D; Norman, G E; Stegailov, V V

    2016-01-01

    Molecular dynamics is applied to calculate diffusion coefficients of n-triacontane C 30 H 62 using Einstein-Smoluchowski and Green-Kubo relations. The displacement 〈Δr 2 〉( t ) has a subdiffusive part 〈Δr 2 〉 ∼ t α , caused by molecular crowding at low temperatures. Longtime asymptotes of 〈v(0)v(t)〉 are collated with the hydrodynamic tail t -3/2 demonstrated for atomic liquids. The influence of these asymptotes on the compliance of Einstein-Smoluchowski and Green-Kubo methods is analyzed. The effects of the force field parameters on the diffusion process are treated. The results are compared with experimental data. (paper)

  15. Shape Changing Nonlocal Molecular Deformations in a Nematic Liquid Crystal

    International Nuclear Information System (INIS)

    Kavitha, L.; Venkatesh, M.; Gopi, D.

    2010-07-01

    The nature of nonlinear molecular deformations in a homeotropically aligned nematic liquid crystal (NLC) is presented. We start from the basic dynamical equation for the director axis of a NLC with elastic deformation mapped onto an integro-differential perturbed Nonlinear Schroedinger equation which includes the nonlocal term. By invoking the modified extended tangent hyperbolic function method aided with symbolic computation, we obtain a series of solitary wave solutions. Under the influence of the nonlocality induced by the reorientation nonlinearity due to fluctuations in the molecular orientation, the solitary wave exhibits shape changing property for different choices of parameters. This intriguing property, as a result of the relation between the coherence of the solitary deformation and the nonlocality, reveals a strong need for deeper understanding in the theory of self-localization in NLC systems. (author)

  16. High density liquid structure enhancement in glass forming aqueous solution of LiCl

    Science.gov (United States)

    Camisasca, G.; De Marzio, M.; Rovere, M.; Gallo, P.

    2018-06-01

    We investigate using molecular dynamics simulations the dynamical and structural properties of LiCl:6H2O aqueous solution upon supercooling. This ionic solution is a glass forming liquid of relevant interest in connection with the study of the anomalies of supercooled water. The LiCl:6H2O solution is easily supercooled and the liquid state can be maintained over a large decreasing temperature range. We performed simulations from ambient to 200 K in order to investigate how the presence of the salt modifies the behavior of supercooled water. The study of the relaxation time of the self-density correlation function shows that the system follows the prediction of the mode coupling theory and behaves like a fragile liquid in all the range explored. The analysis of the changes in the water structure induced by the salt shows that while the salt preserves the water hydrogen bonds in the system, it strongly affects the tetrahedral hydrogen bond network. Following the interpretation of the anomalies of water in terms of a two-state model, the modifications of the oxygen radial distribution function and the angular distribution function of the hydrogen bonds in water indicate that LiCl has the role of enhancing the high density liquid component of water with respect to the low density component. This is in agreement with recent experiments on aqueous ionic solutions.

  17. Phase diagram of supercooled water confined to hydrophilic nanopores

    Science.gov (United States)

    Limmer, David T.; Chandler, David

    2012-07-01

    We present a phase diagram for water confined to cylindrical silica nanopores in terms of pressure, temperature, and pore radius. The confining cylindrical wall is hydrophilic and disordered, which has a destabilizing effect on ordered water structure. The phase diagram for this class of systems is derived from general arguments, with parameters taken from experimental observations and computer simulations and with assumptions tested by computer simulation. Phase space divides into three regions: a single liquid, a crystal-like solid, and glass. For large pores, radii exceeding 1 nm, water exhibits liquid and crystal-like behaviors, with abrupt crossovers between these regimes. For small pore radii, crystal-like behavior is unstable and water remains amorphous for all non-zero temperatures. At low enough temperatures, these states are glasses. Several experimental results for supercooled water can be understood in terms of the phase diagram we present.

  18. Slow Dynamics and Structure of Supercooled Water in Confinement

    Directory of Open Access Journals (Sweden)

    Gaia Camisasca

    2017-04-01

    Full Text Available We review our simulation results on properties of supercooled confined water. We consider two situations: water confined in a hydrophilic pore that mimics an MCM-41 environment and water at interface with a protein. The behavior upon cooling of the α relaxation of water in both environments is well interpreted in terms of the Mode Coupling Theory of glassy dynamics. Moreover, we find a crossover from a fragile to a strong regime. We relate this crossover to the crossing of the Widom line emanating from the liquid-liquid critical point, and in confinement we connect this crossover also to a crossover of the two body excess entropy of water upon cooling. Hydration water exhibits a second, distinctly slower relaxation caused by its dynamical coupling with the protein. The crossover upon cooling of this long relaxation is related to the protein dynamics.

  19. Molecular dynamics simulation of thermophysical properties of undercooled liquid cobalt

    International Nuclear Information System (INIS)

    Han, X J; Wang, J Z; Chen, M; Guo, Z Y

    2004-01-01

    Molecular dynamics simulations with two different embedded-atom-method (EAM) potentials are applied to calculate the density, specific heat and self-diffusion coefficient of liquid cobalt at temperatures above and below the melting temperature. Simulation shows that Pasianot's EAM model of cobalt constructed on the basis of a hcp structure is more successful than Stoop's EAM model in the framework of a fcc structure in predicting the thermophysical properties of liquid cobalt. Simulations with Pasianot's EAM model indicate that the density fits into ρ = 7.49-9.17 x 10 -4 (T- T m ) g cm -3 , and the self-diffusion coefficient is given by D = 1.291 x 10 -7 exp(-48 795.71/RT) m 2 s -1 . Dissimilar to the linear dependence of the density and the Arrhenius dependence of the self-diffusion coefficient on temperature, the specific heat shows almost a constant value of 38.595 ± 0.084 J mol -1 K -1 within the temperature range of simulation. The simulated properties of liquid cobalt are compared with experimental data available. Comparisons show reasonable agreements between the simulated results from Pasianot's EAM model and experimental data

  20. Liquid-vapor coexistence by molecular dynamics simulation

    International Nuclear Information System (INIS)

    Baranyai, Andras; Cummings, Peter T.

    2000-01-01

    We present a simple and consistent molecular dynamics algorithm for determining the equilibrium properties of a bulk liquid and its coexisting vapor phase. The simulation follows the dynamics of the two systems simultaneously while maintaining the volume and the number of particles of the composite system fixed. The thermostat can constrain either the total energy or the temperature at a desired value. Division of the extensive properties between the two phases is governed by the difference of the corresponding intensive state variables. Particle numbers are continuous variables and vary only in virtual sense, i.e., the real sizes of the two systems are the same and do not change during the course of the simulation. Calculation of the chemical potential is separate from the dynamics; thus, one can replace the particle exchange step with other method if it improves the efficiency of the code. (c) 2000 American Institute of Physics

  1. Molecular dynamics simulations of glycerol glass-forming liquid

    International Nuclear Information System (INIS)

    Blieck, J.; Affouard, F.; Bordat, P.; Lerbret, A.; Descamps, M.

    2005-01-01

    Structural and dynamical properties of liquid glycerol have been investigated by Molecular Dynamics simulations. An improved model based on a slight reparametrisation of the all-atoms AMBER force field used in [R. Chelli, P. Procacci, G. Cardini, R.G.D. Valle, S. Califano, Phys. Chem. Chem. Phys. 1 (1999) 871] is presented. The structure remains satisfactory, qualitatively similar to that obtained from the original model. This new model is also found to reproduce significantly better the diffusion coefficient and the correlations times as they can be deduced from neutron spin echo (NSE) experiments. Structural heterogeneities revealed as a pre-peak of the static structure factor S(Q) close to Q ∼ 0.6 A -1 are observed. Our results are also found compatible with predictions of the Mode Coupling Theory

  2. A molecular dynamics study of solid and liquid UO2

    International Nuclear Information System (INIS)

    Sindzingre, P.; Gillan, M.J.

    1988-01-01

    We present an extensive series of molecular dynamics simulations of UO 2 in the solid and liquid states, in which we calculate the ionic diffusion coefficients and some of the important thermodynamic quantities. The simulations are based on a rigid-ion model derived from the new shell model potentials of Jackson and co-workers and make use of recently developed constant-pressure and constant-temperature techniques. The simulations confirm that UO 2 is an oxygen superionic conductor, as suggested by recent neutron scattering experiments. The temperature of the diffuse transition to the superionic regime is in satisfactory agreement with experiment, as is the melting point of the model system. The thermal expansion coefficient, specific heat and bulk modulus for the solid agree well with experiment below about 2500 K but are less satisfactory near the melting point; we suggest that the differences may be due to the effect of electronic excitations. The volume increase on melting and thermodynamic quantities of the liquid are sensitive to details of the inter-ionic potentials and are in only fair agreement with experiment. (author)

  3. Dynamics of supercooled confined water measured by deep inelastic neutron scattering

    Science.gov (United States)

    De Michele, Vincenzo; Romanelli, Giovanni; Cupane, Antonio

    2018-02-01

    In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid-liquid transition of supercooled confined water) on a "wet" sample with hydration h 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually "dry" sample at h 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid-liquid transition hypothesis.

  4. Modeling the liquid-liquid interface and the transfer of a solute by molecular dynamics simulation

    International Nuclear Information System (INIS)

    Hayoun, Marc

    1990-11-01

    Molecular Dynamics method and Lennard-Jones potential functions have been employed to model Liquid-Liquid Interfaces. The variation of the miscibilities between the two liquids is obtained by changing the interaction between the two atomic species. The resulting interfaces have a thickness of about three atomic diameters and are stable on the time scale of the simulation. They have been characterized by the density and pressure profiles. The interfacial tension has also been computed and is of the order of magnitude of experimental values. The diffusion process is anisotropic in the interfacial region: the transverse diffusion coefficient (parallelly to the interface) is higher than the normal one. A qualitative explanation of this behaviour is suggested by considering the pressure tensor. The second part of this work, performed by Molecular Dynamics in the canonical ensemble, is devoted to the kinetic study of the transfer of a solute through the interface. A model of a symmetric interface with an atomic solute has been used. The interaction potential between the solute and the solvents has been built in order to obtain an activation barrier to the transfer. We have computed the mean force exerted by the solvent on the solute as a function of its distance to the interface. The resulting mean force potential corresponds to a free energy difference. The height of the energy barrier involved is about 4 kT. The potential energy and entropy profiles have also been calculated and discussed. The diffusion coefficient of the solute has been computed by equilibrium and non-equilibrium methods. We deduced the friction coefficient of the solvent, which is essential to determine the Kramers transmission coefficient. This coefficient is compared to the one obtained by simulation. Finally, the solute transfer rate constant has been calculated. (author) [fr

  5. Dielectric studies of molecular motions in glassy and liquid nicotine

    Energy Technology Data Exchange (ETDEWEB)

    Kaminski, K [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Paluch, M [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Ziolo, J [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Ngai, K L [Naval Research Laboratory, Washington DC 20375-5320 (United States)

    2006-06-21

    The dielectric permittivity and loss spectra of glassy and liquid states of nicotine have been measured over the frequency range 10{sup -2}-10{sup 9} Hz. The relaxation spectra are similar to common small molecular glass-forming substances, showing the structural {alpha}-relaxation and its precursor, the Johari-Goldstein {beta}-relaxation. The {alpha}-relaxation is well described by the Fourier transform of the Kohlrausch-Williams-Watts stretched exponential function with an approximately constant stretch exponent that is equal to 0.70 as the glass transition temperature is approached. The dielectric {alpha}-relaxation time measured over 11 orders of magnitude cannot be described by a single Vogel-Fulcher-Tamman-Hesse equation. The most probable Johari-Goldstein {beta}-relaxation time determined from the dielectric spectra is in good agreement with the primitive relaxation time of the coupling model calculated from parameters of the structural {alpha}-relaxation. The shape of the dielectric spectra of nicotine is compared with that of other glass-formers having about the same stretch exponent, and they are shown to be nearly isomorphic. The results indicate that the molecular dynamics of nicotine conform to the general pattern found in other glass-formers, and the presence of the universal Johari-Goldstein secondary relaxation, which plays a role in the crystallization of amorphous pharmaceuticals.

  6. Gelation on heating of supercooled gelatin solutions.

    Science.gov (United States)

    Guigo, Nathanaël; Sbirrazzuoli, Nicolas; Vyazovkin, Sergey

    2012-04-23

    Diluted (1.0-1.5 wt%) aqueous gelatin solutions have been cooled to -10 °C at a cooling rate 20 °C min(-1) without freezing and detectable gelation. When heated at a constant heating rate (0.5 -2 °C min(-1)), the obtained supercooled solutions demonstrate an atypical process of gelation that has been characterized by regular and stochastically modulated differential scanning calorimetry (DSC) as well as by isoconversional kinetic analysis. The process is detectable as an exothermic peak in the total heat flow of regular DSC and in the nonreversing heat flow of stochastically modulated DSC. Isoconversional kinetic analysis applied to DSC data reveals that the effective activation energy of the process increases from approximately 75 to 200 kJ mol(-1) as a supercooled solution transforms to gel on continuous heating. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Bulk and interfacial molecular structure near liquid-liquid critical points

    Energy Technology Data Exchange (ETDEWEB)

    Manzanares-Papayanopoulos, Emilio

    2000-09-01

    Critical behaviour occurs when two coexisting phases merge identity without abrupt change in physical properties. The detail of this behaviour is nowadays considered universal, being dominated by the divergence of the correlation length {xi}. Following this universality, the detailed behaviour can be studied experimentally using any convenient system. For that reason, the study of fluids, and in particular fluid mixtures, offers a useful platform since critical behaviour in such systems can often be studied at convenient temperatures and pressures. Although criticality is a consequence of the divergence of {xi}, and so in a sense is a large-scale phenomenon, nevertheless it has an influence on events at molecular level. This aspect of criticality has received relatively little study compared to the enormous effort expended over the past thirty years in elucidating the macroscopic or phenomenological aspects of criticality. The signature of criticality at molecular level is the central theme running through this research.The aim of the work described in this thesis was to investigate the surface and transport properties of near-critical binary liquid mixtures. The surface properties mainly concerned the adsorption and wetting behaviour at the vapour-liquid and liquid-solid interfaces. The transport property studied was the shear viscosity at bulk or macroscopic level and the corresponding property at molecular or microscopic level, the micro viscosity. The work presented in this thesis comprises the experimental measurements and the theoretical interpretations drawn from the results. The experimental work was varied, using both classical and modern techniques. The theoretical interpretation was used as directed towards validating and comparing the results of the experimental programme with the predictions of the current classical critical-state theories. The systems investigated have been mostly alkane + perfluoroalkane mixtures or mixtures with very similar

  8. The structure of molecular liquids. Neutron diffraction and molecular dynamics simulations

    International Nuclear Information System (INIS)

    Bianchi, L.

    2000-05-01

    Neutron diffraction (ND) measurements on liquid methanol (CD 3 OD, CD 3 O(H/D), CD 3 OH) under ambient conditions were performed to obtain the distinct (intra- + inter-molecular), G dist (r) and inter-molecular, G inter (r) radial distribution functions (rdfs) for the three samples. The H/D substitution on hydroxyl-hydrogen (Ho) has been used to extract the partial distribution functions, G XHo (r) (X=C, O, and H - a methyl hydrogen) and G XX (r) at both the distinct and inter-molecular levels from the difference techniques of ND. The O-Ho bond length, which has been the subject of controversy in the past, is found purely from the distinct partial distribution function, G XHo (r) to be 0.98 ± 0.01 A. The C-H distance obtained from the distinct G XX (r) partial is 1.08 ± 0.01 A. These distances determined by fitting an intra-molecular model to the total distinct structure functions are 0.961 ± 0.001 A and 1.096 ± 0.001 A, respectively. The inter-molecular G XX (r) function, dominated by contributions from the methyl groups, apart from showing broad oscillations extending up to ∼14 A is featureless, mainly because of cancellation effects from six contributing pairs. The Ho-Ho partial pair distribution function (pdf), g HoHo (r), determined from the second order difference, shows that only one other Ho atom can be found within a mean Ho-Ho separation of 2.36 A. The average position of the O-Ho hydrogen bond determined for the first time purely from experimental inter-molecular G XHo (r) partial distribution function is found to be at 1.75 ± 0.03 A. The experimental structural results at the partial distribution level are compared with those obtained from molecular dynamics (MD) simulations performed in NVE ensemble by using both 3- and 6-site force field models for the first time in this study. The MD simulations with both the models reproduce the ND rdfs rather well. However, discrepancies begin to appear between the simulated and the experimental partial

  9. Layered interfaces between immiscible liquids studied by density-functional theory and molecular-dynamics simulations.

    Science.gov (United States)

    Geysermans, P; Elyeznasni, N; Russier, V

    2005-11-22

    We present a study of the structure in the interface between two immiscible liquids by density-functional theory and molecular-dynamics calculations. The liquids are modeled by Lennard-Jones potentials, which achieve immiscibility by suppressing the attractive interaction between unlike particles. The density profiles of the liquids display oscillations only in a limited part of the simple liquid-phase diagram (rho,T). When approaching the liquid-vapor coexistence, a significant depletion appears while the layering behavior of the density profile vanishes. By analogy with the liquid-vapor interface and the analysis of the adsorption this behavior is suggested to be strongly related to the drying transition.

  10. Molecular dynamics study of solid-liquid heat transfer and passive liquid flow

    Science.gov (United States)

    Yesudasan Daisy, Sumith

    High heat flux removal is a challenging problem in boilers, electronics cooling, concentrated photovoltaic and other power conversion devices. Heat transfer by phase change is one of the most efficient mechanisms for removing heat from a solid surface. Futuristic electronic devices are expected to generate more than 1000 W/cm2 of heat. Despite the advancements in microscale and nanoscale manufacturing, the maximum passive heat flux removal has been 300 W/cm2 in pool boiling. Such limitations can be overcome by developing nanoscale thin-film evaporation based devices, which however require a better understanding of surface interactions and liquid vapor phase change process. Evaporation based passive flow is an inspiration from the transpiration process that happens in trees. If we can mimic this process and develop heat removal devices, then we can develop efficient cooling devices. The existing passive flow based cooling devices still needs improvement to meet the future demands. To improve the efficiency and capacity of these devices, we need to explore and quantify the passive flow happening at nanoscales. Experimental techniques have not advanced enough to study these fundamental phenomena at the nanoscale, an alternative method is to perform theoretical study at nanoscales. Molecular dynamics (MD) simulation is a widely accepted powerful tool for studying a range of fundamental and engineering problems. MD simulations can be utilized to study the passive flow mechanism and heat transfer due to it. To study passive flow using MD, apart from the conventional methods available in MD, we need to have methods to simulate the heat transfer between solid and liquid, local pressure, surface tension, density, temperature calculation methods, realistic boundary conditions, etc. Heat transfer between solid and fluids has been a challenging area in MD simulations, and has only been minimally explored (especially for a practical fluid like water). Conventionally, an

  11. Variation along liquid isomorphs of the driving force for crystallization

    DEFF Research Database (Denmark)

    Pedersen, Ulf Rørbæk; Adrjanowicz, Karolina; Niss, Kristine

    2017-01-01

    at a reference temperature. More general analysis allows interpretation of experimental data for molecular liquids such as dimethyl phthalate and indomethacin, and suggests that the isomorph scaling exponent γ in these cases is an increasing function of density, although this cannot be seen in measurements......We investigate the variation of the driving force for crystallization of a supercooled liquid along isomorphs, curves along which structure and dynamics are invariant. The variation is weak, and can be predicted accurately for the Lennard-Jones fluid using a recently developed formalism and data...

  12. Empirical molecular-dynamics study of diffusion in liquid semiconductors

    Science.gov (United States)

    Yu, W.; Wang, Z. Q.; Stroud, D.

    1996-11-01

    We report the results of an extensive molecular-dynamics study of diffusion in liquid Si and Ge (l-Si and l-Ge) and of impurities in l-Ge, using empirical Stillinger-Weber (SW) potentials with several choices of parameters. We use a numerical algorithm in which the three-body part of the SW potential is decomposed into products of two-body potentials, thereby permitting the study of large systems. One choice of SW parameters agrees very well with the observed l-Ge structure factors. The diffusion coefficients D(T) at melting are found to be approximately 6.4×10-5 cm2/s for l-Si, in good agreement with previous calculations, and about 4.2×10-5 and 4.6×10-5 cm2/s for two models of l-Ge. In all cases, D(T) can be fitted to an activated temperature dependence, with activation energies Ed of about 0.42 eV for l-Si, and 0.32 or 0.26 eV for two models of l-Ge, as calculated from either the Einstein relation or from a Green-Kubo-type integration of the velocity autocorrelation function. D(T) for Si impurities in l-Ge is found to be very similar to the self-diffusion coefficient of l-Ge. We briefly discuss possible reasons why the SW potentials give D(T)'s substantially lower than ab initio predictions.

  13. Vapor Pressure Plus: An Experiment for Studying Phase Equilibria in Water, with Observation of Supercooling, Spontaneous Freezing, and the Triple Point

    Science.gov (United States)

    Tellinghuisen, Joel

    2010-01-01

    Liquid-vapor, solid-vapor, and solid-liquid-vapor equilibria are studied for the pure substance water, using modern equipment that includes specially fabricated glass cells. Samples are evaporatively frozen initially, during which they typically supercool to -5 to -10 [degrees]C before spontaneously freezing. Vacuum pumping lowers the temperature…

  14. Vibrations of bioionic liquids by ab initio molecular dynamics and vibrational spectroscopy.

    Science.gov (United States)

    Tanzi, Luana; Benassi, Paola; Nardone, Michele; Ramondo, Fabio

    2014-12-26

    Density functional theory and vibrational spectroscopy are used to investigate a class of bioionic liquids consisting of a choline cation and carboxylate anions. Through quantum mechanical studies of motionless ion pairs and molecular dynamics of small portions of the liquid, we have characterized important structural features of the ionic liquid. Hydrogen bonding produces stable ion pairs in the liquid and induces vibrational features of the carboxylate groups comparable with experimental results. Infrared and Raman spectra of liquids have been measured, and main bands have been assigned on the basis of theoretical spectra.

  15. Molecular structure and correlations in liquid D-2-propanol through neutron diffraction

    International Nuclear Information System (INIS)

    Sahoo, A.; Sarkar, S.; Joarder, R.N.; Krishna, P.S.R.

    2003-01-01

    Like t-butanol, 2-propanol molecules are quite big with substantial amount of asymmetry in the structure and so the analysis of the neutron diffraction data is tricky. A modified method of analysis, similar to one for liquid t-butanol, enables extraction of the detailed molecular conformation and intermolecular correlations through neutron diffraction. The pre-peak in the structure function, a signature of chain molecular association together with partially identified inter-molecular correlations yield some information about the nature of possible H-bonded molecular clusters in the liquid state. (author)

  16. Ab Initio Molecular Dynamics Simulations of Furfural at the Liquid-Solid Interface

    OpenAIRE

    Sanwu Wang; Hongli Dang; Wenhua Xue; Darwin Shields; Xin Liu; Friederike C. Jentoft; Daniel E. Resasco

    2013-01-01

    The bonding configuration and the heat of adsorption of a furfural molecule on the Pd(111) surface were determined by ab initio density-functional-theory calculations. The dynamics of pure liquid water, the liquid-solid interface formed by liquid water and the Pd(111) surface, as well as furfural at the water-Pd interface, were investigated by ab initio molecular dynamics simulations at finite temperatures. Calculations and simulations suggest that the bonding configurati...

  17. Molecular interpretation of Trouton's and Hildebrand's rules for the entropy of vaporization of a liquid

    International Nuclear Information System (INIS)

    Green, James A.; Irudayam, Sheeba Jem; Henchman, Richard H.

    2011-01-01

    Research highlights: → A method to calculate a liquid's entropy of vaporization is proposed. → The entropy of vaporisation depends on force magnitudes from computer simulation. → Calculated values agree with experiment, Trouton's rule and Hildebrand's rule. → Free volumes decrease for larger molecules or those with stronger interactions. - Abstract: The entropy of vaporization at a liquid's boiling point is well approximated by Trouton's rule and even more accurately by Hildebrand's rule. A cell method is used here to calculate the entropy of vaporization for a range of liquids by subtracting the entropy of the gas from that of the liquid. The liquid's entropy is calculated from the force magnitudes measured in a molecular dynamics simulation based on the harmonic approximation. The change in rotational entropy is not accounted for except in the case of liquid water. The predicted entropies of vaporization agree well with experiment and Trouton's and Hildebrand's rules for most liquids and for water except other liquids with hydrogen bonds. This supports the idea that molecular rotation is close to ideal at a liquid's boiling point if hydrogen bonds are absent; if they are present, then the rotational entropy gain must be included. The method provides a molecular interpretation of those rules by providing an equation in terms of a molecule's free volume in a liquid which depends on the force magnitudes. Free volumes at each liquid's boiling point are calculated to be ∼1 A 3 for liquids lacking hydrogen bonds, lower at ∼0.3 A 3 for those with hydrogen bonds, and they decrease weakly with increasing molecular size.

  18. Phosphoric acids as amplifiers of molecular chirality in liquid crystalline media

    NARCIS (Netherlands)

    Eelkema, R; Feringa, BL

    2006-01-01

    A new system for the double amplification of the molecular chirality of simple chiral amines in achiral liquid crystalline media is described. It involves a conformationally flexible phosphoric acid based receptor that by binding to chiral amines induces chirality in the liquid crystalline matrix.

  19. Improving the Molecular Ion Signal Intensity for In Situ Liquid SIMS Analysis.

    Science.gov (United States)

    Zhou, Yufan; Yao, Juan; Ding, Yuanzhao; Yu, Jiachao; Hua, Xin; Evans, James E; Yu, Xiaofei; Lao, David B; Heldebrant, David J; Nune, Satish K; Cao, Bin; Bowden, Mark E; Yu, Xiao-Ying; Wang, Xue-Lin; Zhu, Zihua

    2016-12-01

    In situ liquid secondary ion mass spectrometry (SIMS) enabled by system for analysis at the liquid vacuum interface (SALVI) has proven to be a promising new tool to provide molecular information at solid-liquid and liquid-vacuum interfaces. However, the initial data showed that useful signals in positive ion spectra are too weak to be meaningful in most cases. In addition, it is difficult to obtain strong negative molecular ion signals when m/z>200. These two drawbacks have been the biggest obstacle towards practical use of this new analytical approach. In this study, we report that strong and reliable positive and negative molecular signals are achievable after optimizing the SIMS experimental conditions. Four model systems, including a 1,8-diazabicycloundec-7-ene (DBU)-base switchable ionic liquid, a live Shewanella oneidensis biofilm, a hydrated mammalian epithelia cell, and an electrolyte popularly used in Li ion batteries were studied. A signal enhancement of about two orders of magnitude was obtained in comparison with non-optimized conditions. Therefore, molecular ion signal intensity has become very acceptable for use of in situ liquid SIMS to study solid-liquid and liquid-vacuum interfaces. Graphical Abstract ᅟ.

  20. Local elastic expansion model for viscous-flow activation energies of glass-forming molecular liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe; Olsen, Niels Boye; Christensen, Tage Emil

    1996-01-01

    A model for the viscosity of glass-forming molecular liquids is proposed in which a "flow event" requires a local volume increase. The activation energy for a flow event is identified with the work done in shoving aside the surrounding liquid; this work is proportional to the high-frequency shear...

  1. Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface.

    Science.gov (United States)

    Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

    2015-07-07

    The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

  2. Little evidence for dynamic divergences in ultraviscous molecular liquids

    DEFF Research Database (Denmark)

    Hecksher, Tina; Nielsen, Albena; Olsen, Niels Boye

    2008-01-01

    The physics of the ultraviscous liquid phase preceding glass formation continues to pose major problems that remain unsolved. It is actively debated, for instance, whether the marked increase of the relaxation time reflects an underlying phase transition to a state of infinite relaxation time....... To elucidate the empirical evidence for this intriguing scenario, some of the most accurate relaxationtime data available for any class of ultraviscous liquids-those obtained by dielectric relaxation experiments on organic liquids just above the glass transition-were compiled. Analysis of data for 42 liquids...... shows that there is no compelling evidence for the Vogel-Fulcher-Tammann (VFT) prediction that the relaxation time diverges at a finite temperature.We conclude that theories with a dynamic divergence of the VFT formlack a direct experimental basis....

  3. Perspective on the structure of liquid water

    International Nuclear Information System (INIS)

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

    2011-01-01

    Graphical abstract: Liquid water can be described in a fluctuating inhomogeneous picture with two local structural motifs that are spatially separated. At ambient temperatures most molecules favor a closer packing than tetrahedral, with strongly distorted hydrogen bonds giving higher density (yellow), 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 (blue), i.e. 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. Highlights: ► Two components maximizing either enthalpy (tetrahedral, low-density) or entropy (non-specific H-bonding, higher density). ► Interconvert discontinuously and ratio depends on temperature. ► Density fluctuations on 1 nm length scale. ► Increasing size in supercooled region. ► Connection to Widom line and 2nd critical point. - Abstract: 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 in the ambient regime. 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, i.e. 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 and low density liquid. We will discuss the interpretation of X-ray absorption spectroscopy, X-ray emission

  4. The inherent dynamics of a molecular liquid: Geodesic pathways through the potential energy landscape of a liquid of linear molecules

    Science.gov (United States)

    Jacobson, Daniel; Stratt, Richard M.

    2014-05-01

    Because the geodesic pathways that a liquid follows through its potential energy landscape govern its slow, diffusive motion, we suggest that these pathways are logical candidates for the title of a liquid's "inherent dynamics." Like their namesake "inherent structures," these objects are simply features of the system's potential energy surface and thus provide views of the system's structural evolution unobstructed by thermal kinetic energy. This paper shows how these geodesic pathways can be computed for a liquid of linear molecules, allowing us to see precisely how such molecular liquids mix rotational and translational degrees of freedom into their dynamics. The ratio of translational to rotational components of the geodesic path lengths, for example, is significantly larger than would be expected on equipartition grounds, with a value that scales with the molecular aspect ratio. These and other features of the geodesics are consistent with a picture in which molecular reorientation adiabatically follows translation—molecules largely thread their way through narrow channels available in the potential energy landscape.

  5. A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes

    Science.gov (United States)

    Lourenço, Tuanan C.; Zhang, Yong; Costa, Luciano T.; Maginn, Edward J.

    2018-05-01

    Classical molecular dynamics simulations were performed on twelve different ionic liquids containing aprotic heterocyclic anions doped with Li+. These ionic liquids have been shown to be promising electrolytes for lithium ion batteries. Self-diffusivities, lithium transference numbers, densities, and free volumes were computed as a function of lithium concentration. The dynamics and free volume decreased with increasing lithium concentration, and the trends were rationalized by examining the changes to the liquid structure. Of those examined in the present work, it was found that (methyloxymethyl)triethylphosphonium triazolide ionic liquids have the overall best performance.

  6. Supercooling of Water Controlled by Nanoparticles and Ultrasound

    Science.gov (United States)

    Cui, Wei; Jia, Lisi; Chen, Ying; Li, Yi'ang; Li, Jun; Mo, Songping

    2018-05-01

    Nanoparticles, including Al2O3 and SiO2, and ultrasound were adopted to improve the solidification properties of water. The effects of nanoparticle concentration, contact angle, and ultrasonic intensity on the supercooling degree of water were investigated, as well as the dispersion stability of nanoparticles in water during solidification. Experimental results show that the supercooling degree of water is reduced under the combined effect of ultrasound and nanoparticles. Consequently, the reduction of supercooling degree increases with the increase of ultrasonic intensity and nanoparticle concentration and decrease of contact angle of nanoparticles. Moreover, the reduction of supercooling degree caused by ultrasound and nanoparticles together do not exceed the sum of the supercooling degree reductions caused by ultrasound and nanoparticles separately; the reduction is even smaller than that caused by ultrasound individually under certain conditions of controlled nanoparticle concentration and contact angle and ultrasonic intensity. The dispersion stability of nanoparticles during solidification can be maintained only when the nanoparticles and ultrasound together show a superior effect on reducing the supercooling degree of water to the single operation of ultrasound. Otherwise, the aggregation of nanoparticles appears in water solidification, which results in failure. The relationships among the meaningful nanoparticle concentration, contact angle, and ultrasonic intensity, at which the requirements of low supercooling and high stability could be satisfied, were obtained. The control mechanisms for these phenomena were analyzed.

  7. Molecular Dynamics Simulations of Liquid Phosphorus at High Temperature and Pressure

    International Nuclear Information System (INIS)

    Wu Yanning; Zhao Gang; Liu Changsong; Zhu Zhengang

    2008-01-01

    By performing ab initio molecular dynamics simulations, we have investigated the microstructure, dynamical and electronic properties of liquid phosphorus (P) under high temperature and pressure. In our simulations, the calculated coordination number (CN) changes discontinuously with density, and seems to increase rapidly after liquid P is compressed to 2.5 g/cm 3 . Under compression, liquid P shows the first-order liquid-liquid phase transition from the molecular liquid composed of the tetrahedral P 4 molecules to complex polymeric form with three-dimensional network structure, accompanied by the nonmetal to metal transition of the electronic structure. The order parameters Q 6 and Q 4 are sensitive to the microstructural change of liquid P. By calculating diffusion coefficients, we show the dynamical anomaly of liquid P by compression. At lower temperatures, a maximum exists at the diffusion coefficients as a function of density; at higher temperatures, the anomalous behavior is weakened. The excess entropy shows the same phenomena as the diffusion coefficients. By analysis of the angle distribution functions and angular limited triplet correlation functions, we can clearly find that the Peierls distortion in polymeric form of liquid P is reduced by further compression

  8. Investigation of hybrid molecular material prepared by ionic liquid ...

    Indian Academy of Sciences (India)

    Wintec

    Near IR spectral region (1000–2500 nm) shows the elimination of water in the compound which ... 1-Butyl 3-methyl imidazolium bromide; molecular material; phosphotungstic acid; near IR. ..... attributable to the first overtone of hydroxyl groups,.

  9. Induction of Liquid Crystallinity by Self-Assembled Molecular Boxes

    NARCIS (Netherlands)

    Piermattei, A.; Giesbers, M.; Marcelis, A.T.M.; Mendes, E.; Picken, S.J.; Crego-Calama, M.; Reinhoudt, D.N.

    2006-01-01

    In a hierarchical process, three molecules of a calix[4]arene (blue) and six of barbituric or cyanuric acid (green) assemble into double-rosette boxes, which assemble into columns, which in turn assemble into columnar liquid-crystalline phases (see picture). The resulting mesophases have a

  10. Studies on Molecular Interaction in Ternary Liquid Mixtures

    Directory of Open Access Journals (Sweden)

    R. Uvarani

    2010-01-01

    Full Text Available Ultrasonic velocity, density and viscosity for the ternary liquid mixtures of cyclohexanone with 1-propanol and 1-butanol in carbon tetrachloride were measured at 303 K. The acoustical parameters and their excess values were calculated. The trends in the variation of these excess parameters were used to discuss the nature and strength of the interactions present between the component molecules.

  11. Molecular conformation and liquid structure of 2-propanol through ...

    Indian Academy of Sciences (India)

    The neutron diffraction data analysis of deuterated liquid 2-propanol at room temperature to ... 2-Propanol being a large molecule with twelve atomic sites, the conformation analysis is tricky ... A Sahoo1 S Sarkar1 P S R Krishna2 R N Joarder1.

  12. Mass transport thermodynamics in nonisothermal molecular liquid mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Semenov, Semen N [Institute for Biochemical Physics, Russian Academy of Sciences, Moscow (Russian Federation); Schimpf, M E [Department of Chemistry and Biochemistry, Boise State University, Boise, ID (United States)

    2009-10-31

    Mass transport in a nonisothermal binary molecular mixture is systematically discussed in terms of nonequilibrium thermodynamics, which for the first time allows a consistent and unambiguous description of the process. The thermodynamic and hydrodynamic approaches are compared, revealing that nonequilibrium thermodynamics and physicochemical hydrodynamics yield essentially the same results for molecular systems. The applicability limits for the proposed version of the thermodynamic approach are determined for large particles. (methodological notes)

  13. Anomalous structural evolution and liquid fragility signatures in Cu–Zr and Cu–Hf liquids and glasses

    International Nuclear Information System (INIS)

    Mauro, N.A.; Vogt, Adam J.; Johnson, Mark L.; Bendert, James C.; Soklaski, Ryan; Yang, Li; Kelton, K.F.

    2013-01-01

    The results of high energy X-ray scattering studies of equilibrium and supercooled Cu 100−x Zr x (x = 46 and 54) and Cu x Hf 100−x (x = 55 and 60.8) liquids and the corresponding glasses are presented. The liquid data were obtained in a containerless environment using the beamline electrostatic levitation (BESL) technique. The total structure factor and total pair correlation functions were measured as a function of temperature for the liquids, and for the glasses at room temperature. A developing asymmetry in the peak of the first coordination shell in the total pair correlation function suggests chemical ordering in the liquids with cooling. This asymmetry takes the form of two prominent peaks, suggesting two prominent ordering length scales. When the magnitudes of these peaks are extrapolated to the glass transition temperature a discontinuity is observed, indicating that an abrupt increase in the magnitude is required to match the observed peak heights in the glass. This suggests that the structure of the supercooled liquid orders more rapidly near the glass transition temperature, a conclusion that is supported by molecular dynamics simulations. This observed structural evolution of the liquid indicates that the concept of fragility, typically defined from the behavior of viscosity with temperature, has a measurable structural signature as well, which can be observed in X-ray diffraction studies

  14. Electron mobility in nonpolar liquids: the effect of molecular structure, temperature and electric field

    International Nuclear Information System (INIS)

    Schmidt, W.F.

    1977-01-01

    A survey is given on the mobility of excess electrons in liquid hydrocarbons and related compounds. It was found that the mobility is strongly influenced by the molecular structure of the liquid, by the temperature, and by the electric field strength. The mobility in hydrocarbons increases as the shape of the molecule approaches a sphere. The temperature coefficient is positive in most liquids over a limited temperature although exceptions have been observed in liquid methane. The field dependence of the mobility in high mobility liquids (>10 cm 2 V -1 s -1 ) showed a decrease of the mobility at higher field strengths while in low mobility liquids ( 2 V -1 s -1 ) it showed an increase. These results are discussed on the basis of the extended and the localized electron models. The predictions of these theories are compared with the experimental results and conclusions on the validity of the underlying assumptions are drawn. (author)

  15. Microscopic properties of ionic liquid/organic semiconductor interfaces revealed by molecular dynamics simulations.

    Science.gov (United States)

    Yokota, Yasuyuki; Miyamoto, Hiroo; Imanishi, Akihito; Takeya, Jun; Inagaki, Kouji; Morikawa, Yoshitada; Fukui, Ken-Ichi

    2018-05-09

    Electric double-layer transistors based on ionic liquid/organic semiconductor interfaces have been extensively studied during the past decade because of their high carrier densities at low operation voltages. Microscopic structures and the dynamics of ionic liquids likely determine the device performance; however, knowledge of these is limited by a lack of appropriate experimental tools. In this study, we investigated ionic liquid/organic semiconductor interfaces using molecular dynamics to reveal the microscopic properties of ionic liquids. The organic semiconductors include pentacene, rubrene, fullerene, and 7,7,8,8-tetracyanoquinodimethane (TCNQ). While ionic liquids close to the substrate always form the specific layered structures, the surface properties of organic semiconductors drastically alter the ionic dynamics. Ionic liquids at the fullerene interface behave as a two-dimensional ionic crystal because of the energy gain derived from the favorable electrostatic interaction on the corrugated periodic substrate.

  16. Phase behaviour of macromolecular liquid crystalline materials. Computational studies at the molecular level

    International Nuclear Information System (INIS)

    Stimson, Lorna M.

    2003-01-01

    Molecular simulations provide an increasingly useful insight into the static and dynamic characteristics of materials. In this thesis molecular simulations of macro-molecular liquid crystalline materials are reported. The first liquid crystalline material that has been investigated is a side chain liquid crystal polymer (SCLCP). In this study semi-atomistic molecular dynamics simulations have been conducted at a range of temperatures and an aligning potential has been applied to mimic the effect of a magnetic field. In cooling the SCLCP from an isotropic melt, microphase separation was observed yielding a domain structure. The application of a magnetic field to this structure aligns the domains producing a stable smectic mesophase. This is the first study in which mesophases have been observed using an off-lattice model of a SCLCP. The second material that has been investigated is a dendrimer with terminal mesogenic functionalization. Here, a multi-scale approach has been taken with Monte Carlo studies of a single dendrimer molecule in the gas phase at the atomistic level, semi-atomistic molecular dynamics of a single molecule in liquid crystalline solvents and a coarse-grained molecular dynamics study of the dendrimer in the bulk. The coarse-grained model has been developed and parameterized using the results of the atomistic and semi-atomistic work. The single molecule studies showed that the liquid crystalline dendrimer was able to change its structure by conformational changes in the flexible chains that link the mesogenic groups to the core. Structural change was seen under the application of a mean field ordering potential in the gas phase, and in the presence of liquid crystalline solvents. No liquid crystalline phases were observed for the bulk phase studies of the coarse-grained model. However, when the length of the mesogenic units was increased there was some evidence for microphase separation in these systems. (author)

  17. Neutron scattering studies of molecular conformations in liquid crystal polymers

    Science.gov (United States)

    Noirez, L.; Moussa, F.; Cotton, J. P.; Keller, P.; Pépy, G.

    1991-03-01

    A comblike liquid crystal polymer (LPC) is a polymer on which mesogenic molecules have been grafted. It exhibits a succession of liquid crystal phases. Usually the equilibrium conformation of an ordinary polymeric chain corresponds to a maximum entropy, i.e., to an isotropic spherical coil. How does the backbone of a LCP behave in the nematic and smectic field? Small-angle neutron scattering may answer this question. Such measurements are presented here on four different polymers as a function of temperature. An anisotropy of the backbone conformation is found in all these studied compounds, much more pronounced in the smectic phase than in the nematic phase: the backbone spreads more or less perpendicularly to its hanging cores. A comparison with existing theories and a discussion of these results is outlined.

  18. Surface Tension of Supercooled Water: No Inflection Point down to-25 degrees C

    Czech Academy of Sciences Publication Activity Database

    Hrubý, Jan; Vinš, Václav; Mareš, R.; Hykl, Jiří; Kalová, J.

    2014-01-01

    Roč. 5, č. 3 (2014), s. 425-428 ISSN 1948-7185 R&D Projects: GA AV ČR(CZ) IAA200760905; GA ČR(CZ) GPP101/11/P046; GA MŠk(CZ) LG13056 Grant - others:Rada Programu interní podpory projektů mezinárodní spolupráce AV ČR(CZ) M100761201 Institutional support: RVO:61388998 Keywords : liquid * metastable * supercooled Subject RIV: JE - Non-nuclear Energetics, Energy Consumption ; Use Impact factor: 7.458, year: 2014

  19. Experimental investigations on heat content of supercooled sodium acetate trihydrate by a simple heat loss method

    DEFF Research Database (Denmark)

    Kong, Weiqiang; Dannemand, Mark; Johansen, Jakob Berg

    2016-01-01

    Sodium acetate trihydrate is a phase change material that can be used for long term heat storage in solar heating systems because of its relatively high heat of fusion, a melting temperature of 58 °C and its ability to supercool stable. In practical applications sodium acetate trihydrate tend to ......, 0.3–0.5 % (wt.%) Xanthan Gum or 1–2% (wt.%) of some solid or liquid polymers as additives had significantly higher heat contents compared to samples of sodium acetate trihydrate suffering from phase separation....

  20. Application of molecular simulations: Insight into liquid bridging and jetting phenomena

    Directory of Open Access Journals (Sweden)

    I. Nezbeda

    2015-03-01

    Full Text Available Molecular dynamics simulations have been performed on pure liquid water, aqueous solutions of sodium chloride, and polymer solutions exposed to a strong external electric field with the goal to gain molecular insight into the structural response to the field. Several simulation methodologies have been used to elucidate the molecular mechanisms of the processes leading to the formation of liquid bridges and jets (in the production of nanofibers. It is shown that in the established nanoscale structures, the molecules form a chain with their dipole moments oriented parallel to the applied field throughout the entire sample volume. The presence of ions may disturb this structure leading to its ultimate disintegration into droplets; the concentration dependence of the threshold field required to stabilize a liquid column has been determined. Conformational changes of the polymer in the jetting process have also been observed.

  1. Fundamental research on supercooling phenomenon on heat transfer surface

    International Nuclear Information System (INIS)

    Saito, A.; Okawa, S.; Koganezawa, S.

    1991-01-01

    In relation to the problem of supercooling for ice storage devices, experiments on freezing a relatively large volume of supercooled water is carried out. In the experiment, an experimental method to determine a probability of freezing a large volume of supercooled water with a uniform temperature distribution is introduced. It is accomplished by dividing the water into many smaller droplets. In a statistical analysis, a method to improve an accuracy in a case of having a limited number of experiments is introduced, and the probability of freezing is calculated for each degree of supercooling. The average freezing temperature for the experiment is placed just at the extended region of the other researchers results worked on small droplets. By relating the value with the probability of freezing on various kinds of heat transfer surfaces, the probability of freezing which is independent of the surface is calculated. In this paper it is confirmed to be negligible compared with the one on the surface

  2. VIII All-Russian symposium on molecular liquid chromatography and capillary electrophoresis. Program. Summary of reports

    International Nuclear Information System (INIS)

    2001-01-01

    Program and summary of reports of the VIII All-Russian symposium on molecular liquid chromatography and capillary electrophoresis are performed. The meeting took place 15-19 October, 2001 in Moscow. Many problems of liquid and ion exchange chromatography, capillary electrophoresis, thin-layer chromatography have been discussed extensively. Reports covering properties of sorbents and devices for chromatography are incorporated in the collection [ru

  3. Deuteron NMR resolved mesogen vs. crosslinker molecular order and reorientational exchange in liquid single crystal elastomers

    Czech Academy of Sciences Publication Activity Database

    Milavec, J.; Domenici, V.; Zupančič, B.; Rešetič, A.; Bubnov, Alexej; Zalar, B.

    2016-01-01

    Roč. 18, č. 5 (2016), s. 4071-4077 ISSN 1463-9076 R&D Projects: GA ČR GA15-02843S; GA MŠk(CZ) LD14007 Grant - others:EU - ICT(XE) COST Action IC1208 Institutional support: RVO:68378271 Keywords : liquid single crystal elastomer * NMR * liquid crystal * molecular order * monomers Subject RIV: JJ - Other Materials Impact factor: 4.123, year: 2016

  4. NMR determinations of molecular geometries in liquid crystal media

    International Nuclear Information System (INIS)

    Long, R.C.; Goldstein, J.H.

    1983-01-01

    The application of NMR spectroscopy in oriented media to the determination of molecular geometries is illustrated by results for three distinctly different molecules: naphthalene, ethylene oxide and spiropentane. The need for systematic application of vibrational corrections is emphasized and some of the effects associated with the different choices of solvent media are considered

  5. Improvement of imprinting effect of ionic liquid molecularly imprinted polymers by use of a molecular crowding agent.

    Science.gov (United States)

    Jia, Man; Yang, Jian; Sun, Ya Kun; Bai, Xi; Wu, Tao; Liu, Zhao Sheng; Aisa, Haji Akber

    2018-01-01

    We aimed to improve the imprinting effect of ionic liquid molecularly imprinted polymers (MIPs) by use of a molecular crowding agent. The ionic liquid 1-vinyl-3-ethylimidazolium tetrafluoroborate ([VEIm][BF 4 ]) was used as the functional monomer and aesculetin was used as the template molecule in a crowding environment, which was made up of a tetrahydrofuran solution of polystyrene. The ionic liquid MIPs that were prepared in the crowding environment displayed an enhanced imprinting effect. NMR peak shifts of active hydrogen of aesculetin suggested that interaction between the functional monomer and the template could be increased by the use of a crowding agent in the self-assembly process. The retention and selectivity of aesculetin were affected greatly by high molecular crowding, the amount of high molecular weight crowding agent, and the ratio of [VEIm][BF 4 ] to aesculetin. The optimal MIPs were used as solid-phase extraction sorbents to extract aesculetin from Cichorium glandulosum. A calibration curve was obtained with aesculetin concentrations from 0.0005 to 0.05 mg mL -1 (correlation coefficient R 2 of 0.9999, y = 1519x + 0.0923). The limit of quantification was 0.12 μg mL -1 , and the limit of detection was 0.05 μg mL -1 . The absolute recovery of aesculetin was (80 ± 2)% (n = 3), and the purity of aesculetin was (92 ± 0.5)% (n = 5). As a conclusion, molecular crowding is an effective approach to obtain ionic liquid MIPs with high selectivity even in a polar solvent environment.

  6. Surface Tension of Supercooled Water: Inflection Point-Free Course down to 250 K Confirmed Using a Horizontal Capillary Tube

    Czech Academy of Sciences Publication Activity Database

    Vinš, Václav; Hošek, Jan; Hykl, Jiří; Hrubý, Jan

    2017-01-01

    Roč. 62, č. 11 (2017), s. 3823-3832 ISSN 0021-9568 R&D Projects: GA ČR(CZ) GJ15-07129Y Institutional support: RVO:61388998 Keywords : horizontal technique * metastable liquid * supercooled Subject RIV: BJ - Thermodynamics OBOR OECD: Thermodynamics Impact factor: 2.323, year: 2016 http://pubs.acs.org/doi/pdf/10.1021/acs.jced.7b00519

  7. Coexistence of monatomic and diatomic molecular fluid character in liquid gallium

    Energy Technology Data Exchange (ETDEWEB)

    Gong, X.G. (International Centre for Theoretical Physics (ICTP), Trieste (Italy)); Chiarotti, G.L. (International School for Advanced Studies (SISSA), Trieste (Italy) Lab. Tecnologie Avanzate Superfici e Catalisi (TASC), Consorzio Interuniv. Nazionale per la Fisica della Materia (INFM), Trieste (Italy)); Parrinello, M. (IBM Research Div., Zurich Forschungslab., Rueschlikon (Switzerland) International School for Advanced Studies (SISSA), Trieste (Italy)); Tosatti, E. (International School for Advanced Studies (SISSA), Trieste (Italy) International Centre for Theoretical Physics (ICTP), Trieste (Italy) IBM Research Div., Zurich Forschungslab., Rueschlikon (Switzerland))

    1993-02-01

    We have performed an ab initio molecular-dynamics simulation of liquid Ga at high temperature (1000 K). Our results are in good agreement with scattering data and with Knight-shift experiments. A remarkable feature of our findings is the coexistence in the liquid state of metallic and covalent characters. Covalency manifests itself in the appearance of very short-lived Ga-Ga bonds, which represent remnants in the liquid of the crystalline form [alpha]-Ga. We set up a two-fluid scheme which can be used for the analysis of fluids where metallic and covalent characters coexist. (orig.).

  8. Wetting of Liquid Iron in Carbon Nanotubes and on Graphene Sheets: A Molecular Dynamics Study

    International Nuclear Information System (INIS)

    Gao Yu-Feng; Yang Yang; Sun De-Yan

    2011-01-01

    Using molecular dynamics simulations, we study the wetting of liquid iron in a carbon nanotube and on a graphene sheet. It is found that the contact angle of a droplet in a carbon nanotube increases linearly with the increase of wall curvature but is independent of the length of the filled liquid. The contact angle for a droplet on a graphene sheet decreases with the increasing droplet size. The line tension of a droplet on a graphene sheet is also obtained. Detailed studies show that liquid iron near the carbon walls exhibits the ordering tendencies in both the normal and tangential directions. (condensed matter: structure, mechanical and thermal properties)

  9. Coexistence of monatomic and diatomic molecular fluid character in liquid gallium

    International Nuclear Information System (INIS)

    Gong, X.G.; Chiarotti, G.L.; Parrinello, M.; Tosatti, E.

    1993-01-01

    We have performed an ab initio molecular-dynamics simulation of liquid Ga at high temperature (1000 K). Our results are in good agreement with scattering data and with Knight-shift experiments. A remarkable feature of our findings is the coexistence in the liquid state of metallic and covalent characters. Covalency manifests itself in the appearance of very short-lived Ga-Ga bonds, which represent remnants in the liquid of the crystalline form α-Ga. We set up a two-fluid scheme which can be used for the analysis of fluids where metallic and covalent characters coexist. (orig.)

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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 (Hg_1_0In_9_0, Hg_3_0In_7_0_,_. Hg_5_0In_5_0, Hg_7_0In_3_0, and Hg_9_0Pb_1_0) 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.

  11. Ultrasonic Studies of Molecular Interactions in Organic Binary Liquid Mixtures

    Directory of Open Access Journals (Sweden)

    S. Thirumaran

    2010-01-01

    Full Text Available The ultrasonic velocity, density and viscosity have been measured for the mixtures of 1-alkanols such as 1-propanol and 1-butanol with N-N dimethylformamide (DMF at 303 K. The experimental data have been used to calculate the acoustical parameters namely adiabatic compressibility (β, free length (Lf, free volume (Vf and internal pressure (πi. The excess values of the above parameters are also evaluated and discussed in the light of molecular interaction existing in the mixtures. It is obvious that there is a formation of hydrogen bonding between DMF and 1-alkanols. Further, the addition of DMF causes dissociation of hydrogen bonded structure of 1-alkanols. The evaluated excess values confirm that the molecular association is more pronounced in system-II comparing to the system-I.

  12. Theory of molecular crowding in Brownian hard-sphere liquids.

    Science.gov (United States)

    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.

  13. Density scaling of the transport properties of molecular and ionic liquids.

    Science.gov (United States)

    López, Enriqueta R; Pensado, Alfonso S; Comuñas, María J P; Pádua, Agílio A H; Fernández, Josefa; Harris, Kenneth R

    2011-04-14

    Casalini and Roland [Phys. Rev. E 69, 062501 (2004); J. Non-Cryst. Solids 353, 3936 (2007)] and other authors have found that both the dielectric relaxation times and the viscosity, η, of liquids can be expressed solely as functions of the group (TV (γ)), where T is the temperature, V is the molar volume, and γ a state-independent scaling exponent. Here we report scaling exponents γ, for the viscosities of 46 compounds, including 11 ionic liquids. A generalization of this thermodynamic scaling to other transport properties, namely, the self-diffusion coefficients for ionic and molecular liquids and the electrical conductivity for ionic liquids is examined. Scaling exponents, γ, for the electrical conductivities of six ionic liquids for which viscosity data are available, are found to be quite close to those obtained from viscosities. Using the scaling exponents obtained from viscosities it was possible to correlate molar conductivity over broad ranges of temperature and pressure. However, application of the same procedures to the self-diffusion coefficients, D, of six ionic and 13 molecular liquids leads to superpositioning of poorer quality, as the scaling yields different exponents from those obtained with viscosities and, in the case of the ionic liquids, slightly different values for the anion and the cation. This situation can be improved by using the ratio (D∕T), consistent with the Stokes-Einstein relation, yielding γ values closer to those of viscosity.

  14. Nanopore wall-liquid interaction under scope of molecular dynamics study: Review

    Science.gov (United States)

    Tsukanov, A. A.; Psakhie, S. G.

    2017-12-01

    The present review is devoted to the analysis of recent molecular dynamics based on the numerical studies of molecular aspects of solid-fluid interaction in nanoscale channels. Nanopore wall-liquid interaction plays the crucial role in such processes as gas separation, water desalination, liquids decontamination, hydrocarbons and water transport in nano-fractured geological formations. Molecular dynamics simulation is one of the most suitable tools to study molecular level effects occurred in such multicomponent systems. The nanopores are classified by their geometry to four groups: nanopore in nanosheet, nanotube-like pore, slit-shaped nanopore and soft-matter nanopore. The review is focused on the functionalized nanopores in boron nitride nanosheets as novel selective membranes and on the slit-shaped nanopores formed by minerals.

  15. Molecular engineering of chiral colloidal liquid crystals using DNA origami

    Science.gov (United States)

    Siavashpouri, Mahsa; Wachauf, Christian H.; Zakhary, Mark J.; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

    2017-08-01

    Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

  16. Molecular dynamics simulations of hydrophobous ions at the liquid-liquid interfaces: case of dicarbollide anions as synergy agents and of ionic liquids as extracting medium

    International Nuclear Information System (INIS)

    Chevrot, G.

    2008-01-01

    Based on molecular dynamics simulations, we first describe the distribution of dicarbollide salts (CCD - , Mn + ) in concentrated monophasic solutions (water, chloroform, octanol, nitrobenzene) and in the corresponding biphasic 'oil' - water solutions. We point to the importance of surface activity of the CCD - s and of their self-aggregation in water, with marked counterions effects, and we explain the synergistic effect of CCD - s in the Eu 3+ extraction by BTP ligands. In the second part of the thesis we report exploratory simulations on the extraction of Sr 2+ by 18-crown-6 to an hydrophobic ionic liquid ([BMI][PF6]), focusing on the liquid - liquid interface. Analogies and differences with a classical aqueous interface are outlined. (author)

  17. Divergent trend in density versus viscosity of ionic liquid/water mixtures: a molecular view from guanidinium ionic liquids.

    Science.gov (United States)

    Singh, Akhil Pratap; Gardas, Ramesh L; Senapati, Sanjib

    2015-10-14

    Ionic liquids (ILs) have shown great potential in the dissolution and stability of biomolecules when a low-to-moderate quantity of water is added. Hence, determining the thermophysical properties and understanding these novel mixtures at the molecular level are of both fundamental and practical importance. In this context, here we report the synthesis of two nontoxic guanidinium cation based ILs, tetramethylguanidinium benzoate [TMG][BEN] and tetramethylguanidinium salicylate [TMG][SAL], and present a detailed comparison of their thermophysical properties in the presence of water. The results show that the [TMG][SAL]/water mixtures have higher density and higher apparent molar volume, but a lower viscosity and higher compressibility than the [TNG][BEN]/water mixtures. The measured viscosity and compressibility data are explained from ab initio quantum mechanical calculations and liquid-phase molecular dynamics simulations, where salicylate anions of denser [TMG][SAL]/water were found to exist as isolated ions due to intramolecular H-bonding. On the contrary, intermolecular H-bonding among the benzoate anions and their strong tendency to form an extended H-bonding network with water made [TMG][BEN]/water solutions more viscous and less compressible. This study shows the importance of probing these emerging solvents at the molecular-to-atomic level, which could be helpful in their optimal usage for task-specific applications.

  18. Extensive Evaluation of the Conductor-like Screening Model for Real Solvents Method in Predicting Liquid-Liquid Equilibria in Ternary Systems of Ionic Liquids with Molecular Compounds.

    Science.gov (United States)

    Paduszyński, Kamil

    2018-04-12

    A conductor-like screening model for real solvents (COSMO-RS) is nowadays one of the most popular and commonly applied tools for the estimation of thermodynamic properties of complex fluids. The goal of this work is to provide a comprehensive review and analysis of the performance of this approach in calculating liquid-liquid equilibrium (LLE) phase diagrams in ternary systems composed of ionic liquid and two molecular compounds belonging to diverse families of chemicals (alkanes, aromatics, S/N-compounds, alcohols, ketones, ethers, carboxylic acid, esters, and water). The predictions are presented for extensive experimental database, including 930 LLE data sets and more than 9000 data points (LLE tie lines) reported for 779 unique ternary mixtures. An impact of the type of molecular binary subsystem on the accuracy of predictions is demonstrated and discussed on the basis of representative examples. The model's capability of capturing qualitative trends in the LLE distribution ratio and selectivity is also checked for a number of structural effects. Comparative analysis of two levels of quantum chemical theory (BP-TZVP-COSMO vs BP-TZVPD-FINE) for the input molecular data for COSMO-RS is presented. Finally, some general recommendations for the applicability of the model are indicated based on the analysis of the global performance as well as on the results obtained for systems relevant from the point of view of important separation problems.

  19. Changes in permittivity and density of molecular liquids under high pressure.

    Science.gov (United States)

    Kiselev, Vladimir D; Kornilov, Dmitry A; Konovalov, Alexander I

    2014-04-03

    We collected and analyzed the density and permittivity of 57 nonpolar and dipolar molecular liquids at different temperatures (143 sets) and pressures (555 sets). No equation was found that could accurately predict the change to polar liquid permittivity by the change of its density in the range of the pressures and temperatures tested. Consequently, the influence of high hydrostatic pressure and temperature on liquid permittivity may be a more complicated process compared to density changes. The pressure and temperature coefficients of permittivity can be drastically larger than the pressure and temperature coefficients of density, indicating that pressure and particularly temperature significantly affect the structure of molecular liquids. These changes have less influence on the density change but can strongly affect the permittivity change. The clear relationship between the tangent and secant moduli of the permittivity curvatures under pressure for various molecular liquids at different temperatures was obtained, from which one can calculate the Tait equation coefficients from the experimental values of the pressure influence on the permittivity at ambient pressure.

  20. Determination of Fragility in Organic Small Molecular Glass Forming Liquids: Comparison of Calorimetric and Spectroscopic Data and Commentary on Pharmaceutical Importance.

    Science.gov (United States)

    Chakravarty, Paroma; Pandya, Keyur; Nagapudi, Karthik

    2018-03-05

    The fragility index ( m) and conversely the strength parameter ( D) are widely used to categorize glass forming liquids and are used to characterize temperature dependency of viscosity and relaxation time as the supercooled liquid approaches glass transition. The currently used calorimetric methods in pharmaceutical literature lead to wide variability in measured values of m. In this work, a modulated differential scanning calorimetry (DSC) method is introduced that can directly determine m with minimal variability. Although calorimetric fragility is easy to measure due to availability and ease of use of DSC, there is no correlation between calorimetric and dielectric fragility (calculated spectroscopically from relaxation times). In addition, there is also no correlation between calorimetric fragility and the so-called "thermodynamic fragility" that can be calculated using only thermodynamic parameters. No relationship can be found between the crystallization propensity in the supercooled liquid state and D. However, the crystallization propensity shows a reasonable correlation with the Kohlrausch distribution parameter β k , which defines the breadth of the relaxation time distribution.

  1. Determination of low molecular weight thiols using monobromobimane fluorescent labeling and high-performance liquid chromatography

    Science.gov (United States)

    Fahey, Robert C.; Newton, Gerald L.

    1988-01-01

    Methods are described for the preparation and high-performance liquid chromatography (HPLC) analysis of monobromobimane derivatives of low molecular weight thiols in extracts of biological samples. Typical problems encountered in the development and application of these methods are discussed. Analysis of mung bean extract is used as an example.

  2. PREDICTION OF THE MIXING ENTHALPIES OF BINARY LIQUID ALLOYS BY MOLECULAR INTERACTION VOLUME MODEL

    Institute of Scientific and Technical Information of China (English)

    H.W.Yang; D.P.Tao; Z.H.Zhou

    2008-01-01

    The mixing enthalpies of 23 binary liquid alloys are calculated by molecular interaction volume model (MIVM), which is a two-parameter model with the partial molar infinite dilute mixing enthalpies. The predicted values are in agreement with the experimental data and then indicate that the model is reliable and convenient.

  3. Connection between slow and fast dynamics of molecular liquids around the glass transition

    DEFF Research Database (Denmark)

    Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard

    2010-01-01

    The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an “intrinsic” Lindemann criterion for any...

  4. Solid surface vs. liquid surface: nanoarchitectonics, molecular machines, and DNA origami.

    Science.gov (United States)

    Ariga, Katsuhiko; Mori, Taizo; Nakanishi, Waka; Hill, Jonathan P

    2017-09-13

    The investigation of molecules and materials at interfaces is critical for the accumulation of new scientific insights and technological advances in the chemical and physical sciences. Immobilization on solid surfaces permits the investigation of different properties of functional molecules or materials with high sensitivity and high spatial resolution. Liquid surfaces also present important media for physicochemical innovation and insight based on their great flexibility and dynamicity, rapid diffusion of molecular components for mixing and rearrangements, as well as drastic spatial variation in the prevailing dielectric environment. Therefore, a comparative discussion of the relative merits of the properties of materials when positioned at solid or liquid surfaces would be informative regarding present-to-future developments of surface-based technologies. In this perspective article, recent research examples of nanoarchitectonics, molecular machines, DNA nanotechnology, and DNA origami are compared with respect to the type of surface used, i.e. solid surfaces vs. liquid surfaces, for future perspectives of interfacial physics and chemistry.

  5. Communication: High pressure specific heat spectroscopy reveals simple relaxation behavior of glass forming molecular liquid

    DEFF Research Database (Denmark)

    Roed, Lisa Anita; Niss, Kristine; Jakobsen, Bo

    2015-01-01

    The frequency dependent specific heat has been measured under pressure for the molecular glass forming liquid 5-polyphenyl-4-ether in the viscous regime close to the glass transition. The temperature and pressure dependences of the characteristic time scale associated with the specific heat...... is compared to the equivalent time scale from dielectric spectroscopy performed under identical conditions. It is shown that the ratio between the two time scales is independent of both temperature and pressure. This observation is non-trivial and demonstrates the existence of specially simple molecular...... liquids in which different physical relaxation processes are both as function of temperature and pressure/density governed by the same underlying “inner clock.” Furthermore, the results are discussed in terms of the recent conjecture that van der Waals liquids, like the measuredliquid, comply...

  6. On the pressure evolution of dynamic properties of supercooled liquids

    Energy Technology Data Exchange (ETDEWEB)

    Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Roland, C Michael [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Imre, Attila R [KFKI Atomic Energy Research Institute, 1525 Budapest, POB 49 (Hungary)

    2008-06-18

    A pressure counterpart of the Vogel-Fulcher-Tammann (VFT) equation for representing the evolution of dielectric relaxation times or related dynamic properties is discussed: {tau}(P) = {tau}{sub 0}{sup P}exp[D{sub P}{delta}P(P{sub 0}-{delta}P)], where {delta}P = P-P{sub SL}, P{sub 0} is the ideal glass pressure estimation, D{sub P} is the pressure fragility strength coefficient, and the prefactor {tau}{sub 0}{sup P} is related to the relaxation time at the stability limit (P{sub SL}) in the negative pressure domain. The discussion is extended to the Avramov model (AvM) relation {tau}(T,P) = {tau}{sub 0}exp[{epsilon}(T{sub g}(P)/T){sup D}], supplemented with a modified Simon-Glatzel-type equation for the pressure dependence of the glass temperature (T{sub g}(P)), enabling an insight into the negative pressure region. A recently postulated (Dyre 2006 Rev. Mod. Phys. 78 953) comparison between the VFT and the AvM-type descriptions is examined, for both the temperature and the pressure paths. Finally, we address the question 'Does fragility depend on pressure?' from the title of Paluch M et al (2001 J. Chem. Phys. 114 8048) and propose a pressure counterpart for the 'Angell plot'.

  7. Molecular dynamics investigation of tracer diffusion in a simple liquid

    International Nuclear Information System (INIS)

    Ould-Kaddour, F.; Barrat, J.L.

    1991-05-01

    Extensive Molecular-Dynamics (MD) simulations have been carried out for a model trace-solvent system made up of 100 solvent molecules and 8 tracer molecules interacting through truncated Lennard-Jones potentials. The influence of the size ratio between solute and solvent, of their mass ratio and of the solvent viscosity on the diffusivity of a small tracer were investigated. Positive deviations from a Stokes-Einstein behaviour are observed, in qualitative agreement with experimental observations. It was also observed that as tracer and solvent become increasingly dissimilar, their respective dynamics becomes decoupled. We suggest that such decouplings can be interpreted by writing their mobility of the tracer as the sum of two terms, the first one arising from a coupling between tracer dynamics and hydrodynamics modes of the solvent, and the second one describing jump motion in a locally nearly frozen environment. (author). 17 refs, 4 figs, 6 tabs

  8. Water activity in liquid food systems: A molecular scale interpretation.

    Science.gov (United States)

    Maneffa, Andrew J; Stenner, Richard; Matharu, Avtar S; Clark, James H; Matubayasi, Nobuyuki; Shimizu, Seishi

    2017-12-15

    Water activity has historically been and continues to be recognised as a key concept in the area of food science. Despite its ubiquitous utilisation, it still appears as though there is confusion concerning its molecular basis, even within simple, single component solutions. Here, by close examination of the well-known Norrish equation and subsequent application of a rigorous statistical theory, we are able to shed light on such an origin. Our findings highlight the importance of solute-solute interactions thus questioning traditional, empirically based "free water" and "water structure" hypotheses. Conversely, they support the theory of "solute hydration and clustering" which advocates the interplay of solute-solute and solute-water interactions but crucially, they do so in a manner which is free of any estimations and approximations. Copyright © 2017. Published by Elsevier Ltd.

  9. Molecular dynamics simulation of self-diffusion coefficients for liquid metals

    International Nuclear Information System (INIS)

    Ju Yuan-Yuan; Zhang Qing-Ming; Gong Zi-Zheng; Ji Guang-Fu

    2013-01-01

    The temperature-dependent coefficients of self-diffusion for liquid metals are simulated by molecular dynamics methods based on the embedded-atom-method (EAM) potential function. The simulated results show that a good inverse linear relation exists between the natural logarithm of self-diffusion coefficients and temperature, though the results in the literature vary somewhat, due to the employment of different potential functions. The estimated activation energy of liquid metals obtained by fitting the Arrhenius formula is close to the experimental data. The temperature-dependent shear-viscosities obtained from the Stokes—Einstein relation in conjunction with the results of molecular dynamics simulation are generally consistent with other values in the literature. (atomic and molecular physics)

  10. Determination of liquid's molecular interference function based on X-ray diffraction and dual-energy CT in security screening

    International Nuclear Information System (INIS)

    Zhang, Li; YangDai, Tianyi

    2016-01-01

    A method for deriving the molecular interference function (MIF) of an unknown liquid for security screening is presented. Based on the effective atomic number reconstructed from dual-energy computed tomography (CT), equivalent molecular formula of the liquid is estimated. After a series of optimizations, the MIF and a new effective atomic number are finally obtained from the X-ray diffraction (XRD) profile. The proposed method generates more accurate results with less sensitivity to the noise and data deficiency of the XRD profile. - Highlights: • EDXRD combined with dual-energy CT has been utilized for deriving the molecular interference function of an unknown liquid. • The liquid's equivalent molecular formula is estimated based on the effective atomic number reconstructed from dual-energy CT. • The proposed method provides two ways to estimate the molecular interference function: the simplified way and accurate way. • A new effective atomic number of the liquid could be obtained.

  11. The effect of additives on the speed of the crystallization front of xylitol with various degrees of supercooling

    Energy Technology Data Exchange (ETDEWEB)

    Seppaelae, Ari; Merilaeinen, Arttu [Helsinki University of Technology, Department of Energy Technology, Applied Thermodynamics, P.O. Box 4400, 02015 TKK (Finland); Wikstroem, Lisa; Kauranen, Pertti [VTT Technical Research Centre of Finland, Advanced Materials, P.O. Box 1300, 33101 Tampere (Finland)

    2010-07-15

    Some liquids can be kept in a supercooled or supersaturated metastable state for substantially long periods. Such liquids can be applied as long-term heat storage where the latent heat can be released when needed. As xylitol possesses a relatively high value of latent heat and as it can be easily supercooled, it has promising properties for this application. However, the speed of the crystallization of xylitol is low, leading to a low release rate of latent heat. Several additives have been experimentally tested for the purpose of accelerating the crystallization speed. The effect of the additives on the latent heat, on the melting temperatures, and on the long-term durability of the supercooled state was also measured. The highest speeds of the crystallization front, at a temperature of 22 C, were achieved with methanol as an additive leading to speeds 33 times higher in vertical experiments and in 170 times higher in horizontal ones than with pure xylitol. The improved speed of the crystallization front is mostly caused by the methanol flow currents generated as a result of the separation of methanol during crystallization, and to a lesser extent, as a result of the increase in the speed of the growth of the crystals. (author)

  12. New experimental possibilities for the study of the molecular structure and the dynamics of liquids

    International Nuclear Information System (INIS)

    Versmold, H.

    1981-01-01

    The general space-time-pair distribution function G(Rsub(A)(0), Ωsub(A)(0), Rsub(B)(t), Ωsub(B)(t) plays an important role for the theoretical description of liquids. In this report first the relationship between the space-time-pair distribution function and static pair distribution functions, which characterize the liquid structure, and time correlation functions, which can be used to comprehend the dynamics of liquids, will be introduced. As an experimental method, which is particularly suited to determine the static pair distribution function, coherent neutron scattering is discussed. The power of this method for the determination of the liquid structure is demonstrated by considering the examples of a fused salt and a molecular liquid. For investigations of the dynamics of liquids incoherent neutron scattering and several spectroscopic experiments have been in use during the last few years. The relationship between these experiments and time correlation functions is presented. A discussion concerning the possibility to study translational and rotational dynamics by incoherent neutron scattering follows. Finally, by referring to a depolarized Rayleigh experiment, the relationship between spectroscopic experiments and orientational correlation functions, which describe the reorientational dynamics in liquids, is illustrated. (orig.)

  13. Effects of molecular structure on microscopic heat transport in chain polymer liquids

    International Nuclear Information System (INIS)

    Matsubara, Hiroki; Kikugawa, Gota; Ohara, Taku; Bessho, Takeshi; Yamashita, Seiji

    2015-01-01

    In this paper, we discuss the molecular mechanism of the heat conduction in a liquid, based on nonequilibrium molecular dynamics simulations of a systematic series of linear- and branched alkane liquids, as a continuation of our previous study on linear alkane [T. Ohara et al., J. Chem. Phys. 135, 034507 (2011)]. The thermal conductivities for these alkanes in a saturated liquid state at the same reduced temperature (0.7T c ) obtained from the simulations are compared in relation to the structural difference of the liquids. In order to connect the thermal energy transport characteristics with molecular structures, we introduce the new concept of the interatomic path of heat transfer (atomistic heat path, AHP), which is defined for each type of inter- and intramolecular interaction. It is found that the efficiency of intermolecular AHP is sensitive to the structure of the first neighbor shell, whereas that of intramolecular AHP is similar for different alkane species. The dependence of thermal conductivity on different lengths of the main and side chain can be understood from the natures of these inter- and intramolecular AHPs

  14. Effects of molecular structure on microscopic heat transport in chain polymer liquids

    Energy Technology Data Exchange (ETDEWEB)

    Matsubara, Hiroki, E-mail: matsubara@microheat.ifs.tohoku.ac.jp; Kikugawa, Gota; Ohara, Taku [Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Bessho, Takeshi; Yamashita, Seiji [Higashifuji Technical Center, Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan)

    2015-04-28

    In this paper, we discuss the molecular mechanism of the heat conduction in a liquid, based on nonequilibrium molecular dynamics simulations of a systematic series of linear- and branched alkane liquids, as a continuation of our previous study on linear alkane [T. Ohara et al., J. Chem. Phys. 135, 034507 (2011)]. The thermal conductivities for these alkanes in a saturated liquid state at the same reduced temperature (0.7T{sub c}) obtained from the simulations are compared in relation to the structural difference of the liquids. In order to connect the thermal energy transport characteristics with molecular structures, we introduce the new concept of the interatomic path of heat transfer (atomistic heat path, AHP), which is defined for each type of inter- and intramolecular interaction. It is found that the efficiency of intermolecular AHP is sensitive to the structure of the first neighbor shell, whereas that of intramolecular AHP is similar for different alkane species. The dependence of thermal conductivity on different lengths of the main and side chain can be understood from the natures of these inter- and intramolecular AHPs.

  15. Visualization of the collective vortex-like motions in liquid argon and water: Molecular dynamics simulation

    Science.gov (United States)

    Anikeenko, A. V.; Malenkov, G. G.; Naberukhin, Yu. I.

    2018-03-01

    We propose a new measure of collectivity of molecular motion in the liquid: the average vector of displacement of the particles, ⟨ΔR⟩, which initially have been localized within a sphere of radius Rsph and then have executed the diffusive motion during a time interval Δt. The more correlated the motion of the particles is, the longer will be the vector ⟨ΔR⟩. We visualize the picture of collective motions in molecular dynamics (MD) models of liquids by constructing the ⟨ΔR⟩ vectors and pinning them to the sites of the uniform grid which divides each of the edges of the model box into equal parts. MD models of liquid argon and water have been studied by this method. Qualitatively, the patterns of ⟨ΔR⟩ vectors are similar for these two liquids but differ in minor details. The most important result of our research is the revealing of the aggregates of ⟨ΔR⟩ vectors which have the form of extended flows which sometimes look like the parts of vortices. These vortex-like clusters of ⟨ΔR⟩ vectors have the mesoscopic size (of the order of 10 nm) and persist for tens of picoseconds. Dependence of the ⟨ΔR⟩ vector field on parameters Rsph, Δt, and on the model size has been investigated. This field in the models of liquids differs essentially from that in a random-walk model.

  16. Effects of PVA(Polyvinyl Alcohol) on Supercooling Phenomena of Water

    Science.gov (United States)

    Kumano, Hiroyuki; Saito, Akio; Okawa, Seiji; Takizawa, Hiroshi

    In this paper, effects of polymer additive on supercooling of water were investigated experimentally. Poly-vinyl alcohol (PVA) were used as the polymer, and the samples were prepared by dissolving PVA in ultra pure water. Concentration, degree of polymerization and saponification of PVA were varied as the experimental parameters. The sample was cooled, and the temperature at the instant when ice appears was measured. Since freezing of supercooled water is statistical phenomenon, many experiments were carried out and average degrees of supercooling were obtained for each experimental condition. As the result, it was found that PVA affects nucleation of supercooling and the degree of supercooling increases by adding the PVA. Especially, it is found that the average degree of supercooling increases and the standard deviation of average degree of supercooling decreases with increase of degree of saponification of PVA. However, the average degree of supercooling are independent of the degree of polymerization of PVA in the range of this study.

  17. Molecular motions in a viscous organic liquid: ferrocene in cold butyl phthalate

    International Nuclear Information System (INIS)

    Ruby, S.L.; Zabransky, B.J.; Flinn, P.A.

    1976-01-01

    The two main purposes of this work were to learn (a) if rotational diffusion can be seen along with translational, and (b) is [x(T) 2 ] unusual as the sample is heated from a glass to a liquid. Our observations show that (a) rotational molecular diffusion is not likely ever to be observed by quadrupole relaxation and (b) that there is indeed a fast increase in [x 2 ] above T/sub g/. This increase is correlated with a rapid and linear increase of the number of ''soft modes'' for the liquid above the glass transition temperature

  18. Super-cool Dark Matter arXiv

    CERN Document Server

    Hambye, Thomas; Teresi, Daniele

    In dimension-less theories of dynamical generation of the weak scale, the Universe can undergo a period of low-scale inflation during which all particles are massless and super-cool. This leads to a new mechanism of generation of the cosmological Dark Matter (DM) relic density: super-cooling can easily suppress the amount of DM to the desired level. This is achieved for TeV-scale DM, if super-cooling ends when quark condensates form at the QCD phase transition. Along this scenario, the baryon asymmetry can be generated either at the phase transition or through leptogenesis. We show that the above mechanism takes place in old and new dimension-less models.

  19. Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man's land

    Science.gov (United States)

    Ni, Yicun; Hestand, Nicholas J.; Skinner, J. L.

    2018-05-01

    According to the liquid-liquid critical point (LLCP) hypothesis, there are two distinct phases of supercooled liquid water, namely, high-density liquid and low-density liquid, separated by a coexistence line that terminates in an LLCP. If the LLCP is real, it is located within No Man's Land (NML), the region of the metastable phase diagram that is difficult to access using conventional experimental techniques due to rapid homogeneous nucleation to the crystal. However, a recent ingenious experiment has enabled measurement of the diffusion constant deep inside NML. In the current communication, these recent measurements are compared, with good agreement, to the diffusion constant of E3B3 water, a classical water model that explicitly includes three-body interactions. The behavior of the diffusion constant as the system crosses the Widom line (the extension of the liquid-liquid coexistence line into the one-phase region) is analyzed to derive information about the presence and location of the LLCP. Calculations over a wide range of temperatures and pressures show that the new experimental measurements are consistent with an LLCP having a critical pressure of over 0.6 kbar.

  20. Synergistic effect of dicarbollide anions in liquid-liquid extraction: a molecular dynamics study at the octanol-water interface.

    Science.gov (United States)

    Chevrot, G; Schurhammer, R; Wipff, G

    2007-04-28

    We report a molecular dynamics study of chlorinated cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)Cl(3))(2)Co](-)"CCD(-)" in octanol and at the octanol-water interface, with the main aim to understand why these hydrophobic species act as strong synergists in assisted liquid-liquid cation extraction. Neat octanol is quite heterogeneous and is found to display dual solvation properties, allowing to well solubilize CCD(-), Cs(+) salts in the form of diluted pairs or oligomers, without displaying aggregation. At the aqueous interface, octanol behaves as an amphiphile, forming either monolayers or bilayers, depending on the initial state and confinement conditions. In biphasic octanol-water systems, CCD(-) anions are found to mainly partition to the organic phase, thus attracting Cs(+) or even more hydrophilic counterions like Eu(3+) into that phase. The remaining CCD(-) anions adsorb at the interface, but are less surface active than at the chloroform interface. Finally, we compare the interfacial behavior of the Eu(BTP)(3)(3+) complex in the absence and in the presence of CCD(-) anions and extractant molecules. It is found that when the CCD(-)'s are concentrated enough, the complex is extracted to the octanol phase. Otherwise, it is trapped at the interface, attracted by water. These results are compared to those obtained with chloroform as organic phase and discussed in the context of synergistic effect of CCD(-) in liquid-liquid extraction, pointing to the importance of dual solvation properties of octanol and of the hydrophobic character of CCD(-) for synergistic extraction of cations.

  1. Study of Molecular Interactions in Binary Liquid Mixtures by Acoustical Method at 303K

    Directory of Open Access Journals (Sweden)

    P. Paul Divakar

    2012-01-01

    Full Text Available Ultrasonic velocity and density measurements were made in two binary liquid mixtures Isopropyl acetate (IPA and Isobutyl acetate (IBA with cyclohexanone (CY as a common component at 303K, at fixed frequency of 2MHz using single crystal variable path interferometer and specific gravity bottle respectively. The experimental data have been used to calculate the acoustic impedance, adiabatic compressibility, inter molecular free length and molar volume. The excess thermodynamic parameters have been evaluated and discussed in the light of molecular interactions.

  2. Experiment-scale molecular simulation study of liquid crystal thin films

    Science.gov (United States)

    Nguyen, Trung Dac; Carrillo, Jan-Michael Y.; Matheson, Michael A.; Brown, W. Michael

    2014-03-01

    Supercomputers have now reached a performance level adequate for studying thin films with molecular detail at the relevant scales. By exploiting the power of GPU accelerators on Titan, we have been able to perform simulations of characteristic liquid crystal films that provide remarkable qualitative agreement with experimental images. We have demonstrated that key features of spinodal instability can only be observed with sufficiently large system sizes, which were not accessible with previous simulation studies. Our study emphasizes the capability and significance of petascale simulations in providing molecular-level insights in thin film systems as well as other interfacial phenomena.

  3. Thermophysical properties of liquid carbon dioxide under shock compressions: quantum molecular dynamic simulations.

    Science.gov (United States)

    Wang, Cong; Zhang, Ping

    2010-10-07

    Quantum molecular dynamics were used to calculate the equation of state, electrical, and optical properties of liquid carbon dioxide along the Hugoniot at shock pressures up to 74 GPa. The principal Hugoniot derived from the calculated equation of state is in good agreement with experimental results. Molecular dissociation and recombination are investigated through pair correlation functions and decomposition of carbon dioxide is found to be between 40 and 50 GPa along the Hugoniot, where nonmetal-metal transition is observed. In addition, the optical properties of shock compressed carbon dioxide are also theoretically predicted along the Hugoniot.

  4. Molecular-level mechanisms of vibrational frequency shifts in a polar liquid.

    Science.gov (United States)

    Morales, Christine M; Thompson, Ward H

    2011-06-16

    A molecular-level analysis of the origins of the vibrational frequency shifts of the CN stretching mode in neat liquid acetonitrile is presented. The frequency shifts and infrared spectrum are calculated using a perturbation theory approach within a molecular dynamics simulation and are in good agreement with measured values reported in the literature. The resulting instantaneous frequency of each nitrile group is decomposed into the contributions from each molecule in the liquid and by interaction type. This provides a detailed picture of the mechanisms of frequency shifts, including the number of surrounding molecules that contribute to the shift, the relationship between their position and relative contribution, and the roles of electrostatic and van der Waals interactions. These results provide insight into what information is contained in infrared (IR) and Raman spectra about the environment of the probed vibrational mode. © 2011 American Chemical Society

  5. Infrared Spectroscopy as Molecular Probe of the Macroscopic Metal-Liquid Interface

    Directory of Open Access Journals (Sweden)

    Johannes Kiefer

    2017-11-01

    Full Text Available Metal-liquid interfaces are of the utmost importance in a number of scientific areas, including electrochemistry and catalysis. However, complicated analytical methods and sample preparation are usually required to study the interfacial phenomena. We propose an infrared spectroscopic approach that enables investigating the molecular interactions at the interface, but needing only minimal or no sample preparation. For this purpose, the internal reflection element (IRE is wetted with a solution as first step. Second, a small plate of the metal of interest is put on top and pressed onto the IRE. The tiny amount of liquid that is remaining between the IRE and the metal is sufficient to produce an IR spectrum with good signal to noise ratio, from which information about molecular interactions, such as hydrogen bonding, can be deduced. Proof-of-concept experiments were carried out with aqueous salt and acid solutions and an aluminum plate.

  6. Electro-suppression of water nano-droplets' solidification in no man's land: Electromagnetic fields' entropic trapping of supercooled water

    Science.gov (United States)

    Nandi, Prithwish K.; Burnham, Christian J.; English, Niall J.

    2018-01-01

    Understanding water solidification, especially in "No Man's Land" (NML) (150 K < T < 235 K) is crucially important (e.g., upper-troposphere cloud processes) and challenging. A rather neglected aspect of tropospheric ice-crystallite formation is inevitably present electromagnetic fields' role. Here, we employ non-equilibrium molecular dynamics of aggressively quenched supercooled water nano-droplets in the gas phase under NML conditions, in externally applied electromagnetic (e/m) fields, elucidating significant differences between effects of static and oscillating fields: although static fields induce "electro-freezing," e/m fields exhibit the contrary - solidification inhibition. This anti-freeze action extends not only to crystal-ice formation but also restricts amorphisation, i.e., suppression of low-density amorphous ice which forms otherwise in zero-field NML environments. E/m-field applications maintain water in the deeply supercooled state in an "entropic trap," which is ripe for industrial impacts in cryo-freezing, etc.

  7. Connection between slow and fast dynamics of molecular liquids around the glass transition

    International Nuclear Information System (INIS)

    Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard; Russo, Daniela; Dyre, Jeppe; Alba-Simionesco, Christiane

    2010-01-01

    The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an 'intrinsic' Lindemann criterion for any given liquid. A one-to-one connection between the MSD's temperature dependence and the liquid's fragility is found when the MSD is evaluated on a time scale of ∼4 ns, but does not hold when the MSD is evaluated at shorter times. The findings are discussed in terms of the elastic model and the role of relaxations, and the correlations between slow and fast dynamics are addressed.

  8. Towards Molecular Dynamics Simulations of Chiral Room-Temperature Ionic Liquids

    Czech Academy of Sciences Publication Activity Database

    Lísal, Martin; Chval, Z.; Storch, Jan; Izák, Pavel

    2014-01-01

    Roč. 189, SI (2014), s. 85-94 ISSN 0167-7322 R&D Projects: GA ČR(CZ) GAP106/12/0569; GA MŠk LH12020 Institutional support: RVO:67985858 Keywords : chiral room-temperature ionic liquid * molecular dynamics simulation * non-polarizable fully flexible all-atom force field Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.515, year: 2014

  9. Evaporation characteristics of thin film liquid argon in nano-scale confinement: A molecular dynamics study

    Science.gov (United States)

    Hasan, Mohammad Nasim; Shavik, Sheikh Mohammad; Rabbi, Kazi Fazle; Haque, Mominul

    2016-07-01

    Molecular dynamics simulation has been carried out to explore the evaporation characteristics of thin liquid argon film in nano-scale confinement. The present study has been conducted to realize the nano-scale physics of simultaneous evaporation and condensation inside a confined space for a three phase system with particular emphasis on the effect of surface wetting conditions. The simulation domain consisted of two parallel platinum plates; one at the top and another at the bottom. The fluid comprised of liquid argon film at the bottom plate and vapor argon in between liquid argon and upper plate of the domain. Considering hydrophilic and hydrophobic nature of top and bottom surfaces, two different cases have been investigated: (i) Case A: Both top and bottom surfaces are hydrophilic, (ii) Case B: both top and bottom surfaces are hydrophobic. For all cases, equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. Then the lower wall was set to four different temperatures such as 110 K, 120 K, 130 K and 140 K to perform non-equilibrium molecular dynamics (NEMD). The variation of temperature and density as well as the variation of system pressure with respect to time were closely monitored for each case. The heat fluxes normal to top and bottom walls were estimated and discussed to illuminate the effectiveness of heat transfer in both hydrophilic and hydrophobic confinement at various boundary temperatures of the bottom plate.

  10. Dielectric relaxation spectra of liquid crystals in relation to molecular structure

    International Nuclear Information System (INIS)

    Wrobel, S.

    1986-07-01

    The dielectric spectra obtained for some members of two homologous series, i.e. for di-alkoxyazoxybenzenes and penthyl-alkoxythiobenzoates, are discussed qualitatively on the basis of the Nordio-Rigatti-Segre diffusion model. It is additionally assumed that the molecular reorientations take place about the principal axes of the inertia tensor. The distribution of correlation times, which is strongly temperature dependent in the vicinity of the clearing point, is interpreted as being caused by fluctuations of the principal axes frame which are due to conformation changes inside the end chains. The Bauer equation is used to describe both principal molecular reorientations, i.e. the reorientations about the long and short axis, observed in liquid crystalline structure by means of dielectric relaxation methods. The energies and entropies of activation have been computed for both principal reorientations. The differences between the high frequency limit of the dielectric permittivity and the refractive index squared of liquid crystals are explained in terms of two librational motions of the molecules observed by other experimental techniques, viz. far infra-red, Raman and inelastic neutron scattering spectroscopies, and found in this work on the basis of dielectrically measured energy barriers. It has been shown qualitatively that intramolecular libratory motions greatly effect the high frequency dielectric spectrum. Finally, molecular motions in liquid crystals are divided into two types: coherent and incoherent. 127 refs., 56 figs., 17 tabs. (author)

  11. Molecular dynamics simulations of surfactant and nanoparticle self-assembly at liquid-liquid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Luo Mingxiang; Dai, Lenore L [Department of Chemical Engineering, Texas Tech University, Lubbock, TX 79409 (United States)

    2007-09-19

    We have performed molecular dynamics (MD) simulations to investigate self-assembly at water-trichloroethylene (TCE) interfaces with the emphasis on systems containing modified hydrocarbon nanoparticles (1.2 nm in diameter) and sodium dodecyl sulfate (SDS) surfactants. The nanoparticles and surfactants were first distributed randomly in the water phase. The MD simulations have clearly shown the progress of migration and final equilibrium of the SDS molecules at the water-TCE interfaces with the nanoparticles either at or in the vicinity of the interfaces. One unique feature is the 'attachment' of surfactant molecules to the nanoparticle clusters in the water phase followed by the 'detachment' at the water-TCE interfaces. At low concentrations of surfactants, the surfactants and nanoparticles co-equilibrate at the interfaces. However, the surfactants, at high concentrations, competitively dominate the interfaces and deplete nanoparticles away from the interfaces. The interfacial properties, such as interfacial thickness and interfacial tension, are significantly influenced by the presence of the surfactants, but not the nanoparticles. The order of the surfactants at the interfaces increases with increasing surfactant concentration, but is independent of nanoparticle concentration. Finally, the simulation has shown that surfactants can aggregate along the water-TCE interfaces, with and without the presence of nanoparticles.

  12. Droplet-Sizing Liquid Water Content Sensor, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Icing is one of the most significant hazards to aircraft. A sizing supercooled liquid water content (SSLWC) sonde is being developed to meet a directly related need...

  13. Substrate Dependence of the Freezing Dynamics of Supercooled Water Films: A High-Speed Optical Microscope Study.

    Science.gov (United States)

    Pach, E; Rodriguez, L; Verdaguer, A

    2018-01-18

    The freezing of supercooled water films on different substrates was investigated using a high-speed camera coupled to an optical microscope, obtaining details of the freezing process not described in the literature before. We observed the two well known freezing stages (fast dendritic growth and slow freezing of the water liquid left after the dendritic growth), but we separated the process into different phenomena that were studied separately: two-dimensional dendrite growth on the substrate interface, vertical dendrite growth, formation and evolution of ice domains, trapping of air bubbles and freezing of the water film surface. We found all of these processes to be dependent on both the supercooling temperature and the substrate used. Ice dendrite (or ice front) growth during the first stage was found to be dependent on thermal properties of the substrate but could not be unequivocally related to them. Finally, for low supercooling, a direct relationship was observed between the morphology of the dendrites formed in the first stage, which depends on the substrate, and the roughness and the shape of the surface of the ice, when freezing of the film was completed. This opens the possibility of using surfaces and coatings to control ice morphology beyond anti-icing properties.

  14. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    Energy Technology Data Exchange (ETDEWEB)

    Samin, Adib; Li, Xiang; Zhang, Jinsuo [Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States); Mariani, R. D. [Idaho National Laboratory, Materials and Fuels Complex, Idaho Falls, Idaho 83415 (United States); Unal, Cetin [Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, New Mexico 87545 (United States)

    2015-12-21

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10{sup −9} m{sup 2}/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  15. Designs of Plasmonic Metamasks for Photopatterning Molecular Orientations in Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Yubing Guo

    2016-12-01

    Full Text Available Aligning liquid crystal (LC molecules into spatially non-uniform orientation patterns is central to the functionalities of many emerging LC devices. Recently, we developed a new projection photopatterning technique by using plasmonic metamasks (PMMs, and demonstrated high-resolution and high-throughput patterning of molecular orientations into arbitrary patterns. Here we present comparisons between two different types of metamask designs: one based on curvilinear nanoslits in metal films; the other based on rectangular nanoapertures in metal films. By using numerical simulations and experimental studies, we show that the PMMs based on curvilinear nanoslits exhibit advantages in their broadband and high optical transmission, while face challenges in mask designing for arbitrary molecular orientations. In contrast, the PMMs based on nanoapertures, though limited in optical transmission, present the great advantage of allowing for patterning arbitrary molecular orientation fields.

  16. The Oseen-Frank Limit of Onsager's Molecular Theory for Liquid Crystals

    Science.gov (United States)

    Liu, Yuning; Wang, Wei

    2018-03-01

    We study the relationship between Onsager's molecular theory, which involves the effects of nonlocal molecular interactions and the Oseen-Frank theory for nematic liquid crystals. Under the molecular setting, we prove the existence of global minimizers for the generalized Onsager's free energy, subject to a nonlocal boundary condition which prescribes the second moment of the number density function near the boundary. Moreover, when the re-scaled interaction distance tends to zero, the global minimizers will converge to a uniaxial distribution predicted by a minimizing harmonic map. This is achieved through the investigations of the compactness property and the boundary behaviors of the corresponding second moments. A similar result is established for critical points of the free energy that fulfill a natural energy bound.

  17. Liquid-liquid phase transition in Stillinger-Weber silicon

    International Nuclear Information System (INIS)

    Beaucage, Philippe; Mousseau, Normand

    2005-01-01

    It was recently demonstrated that Stillinger-Weber silicon undergoes a liquid-liquid first-order phase transition deep into the supercooled region (Sastry and Angell 2003 Nat. Mater. 2 739). Here we study the effects of perturbations on this phase transition. We show that the order of the liquid-liquid transition changes with negative pressure. We also find that the liquid-liquid transition disappears when the three-body term of the potential is strengthened by as little as 5%. This implies that the details of the potential could affect strongly the nature and even the existence of the liquid-liquid phase

  18. Molecular interactions and thermal transport in ionic liquids with carbon nanomaterials.

    Science.gov (United States)

    França, João M P; Nieto de Castro, Carlos A; Pádua, Agílio A H

    2017-07-05

    We used molecular dynamics simulation to study the effect of suspended carbon nanomaterials, nanotubes and graphene sheets, on the thermal conductivity of ionic liquids, an issue related to understanding the properties of nanofluids. One important aspect that we developed is an atomistic model of the interactions between the organic ions and carbon nanomaterials, so we did not rely on existing force fields for small organic molecules or assume simple combining rules to describe the interactions at the liquid/material interface. Instead, we used quantum calculations with a density functional suitable for non-covalent interactions to parameterize an interaction model, including van der Waals terms and also atomic partial charges on the materials. We fitted a n-m interaction potential function with n values of 9 or 10 and m values between 5 and 8, so a 12-6 Lennard-Jones function would not fit the quantum calculations. For the atoms of ionic liquids and carbon nanomaterials interacting among themselves, we adopted existing models from the literature. We studied the imidazolium ionic liquids [C 4 C 1 im][SCN], [C 4 C 1 im][N(CN) 2 ], [C 4 C 1 im][C(CN) 3 ] and [C 4 C 1 im][(CF 3 SO 2 ) 2 N]. Attraction is stronger for cations (than for anions) above and below the π-system of the nanomaterials, whereas anions show stronger attraction for the hydrogenated edges. The ordering of ions around and inside (7,7) and (10,10) single-walled nanotubes, and near a stack of graphene sheets, was analysed in terms of density distribution functions. We verified that anions are found, as well as cations, in the first interfacial layer interacting with the materials, which is surprising given the interaction potential surfaces. The thermal conductivity of the ionic liquids and of composite systems containing one nanotube or one graphene stack in suspension was calculated using non-equilibrium molecular dynamics. Thermal conductivity was calculated along the axis of the nanotube and

  19. Effect of molecular interactions on retention and selectivity in reversed-phase liquid chromatography.

    Science.gov (United States)

    Szepesy, László

    2002-06-25

    The linear solvation energy relationships (LSERs) have been applied in the last years for description and prediction of retention and selectivity in reversed-phase liquid chromatography with good results. Widely different stationary phases have been compared and characterized by LSERs. In recent publications the influence of the type of the organic moderator and the composition of the mobile phase have also been described. However, the influence of the molecular properties of the solutes to be separated has never been discussed. According to the LSER model variation in retention factors (log k) with solute structure can be related to their potential for various intermolecular interactions. The retention factor is given as the sum of the terms of the LSER equation representing various types of molecular interactions. For this reason the influence of the structure and molecular properties of the solutes to be separated can also be investigated using the LSER equation. In this study we shall demonstrate how the specific molecular interactions influence chromatographic retention and selectivity. We intend to show that retention and selectivity depend on all participants of the system. In addition to the structure and properties of the stationary phase and the type and composition of the mobile phase the molecular properties of the solutes, characterized by the solvation parameters, will also influence the type and extent of the various molecular interactions governing retention and selectivity.

  20. Analysis of supercooling activity of tannin-related polyphenols.

    Science.gov (United States)

    Kuwabara, Chikako; Wang, Donghui; Endoh, Keita; Fukushi, Yukiharu; Arakawa, Keita; Fujikawa, Seizo

    2013-08-01

    Based on the discovery of novel supercooling-promoting hydrolyzable gallotannins from deep supercooling xylem parenchyma cells (XPCs) in Katsura tree (see Wang et al. (2012) [38]), supercooling capability of a wide variety of tannin-related polyphenols (TRPs) was examined in order to find more effective supercooling-promoting substances for their applications. The TRPs examined were single compounds including six kinds of hydrolyzable tannins, 11 kinds of catechin derivatives, two kinds of structural analogs of catechin and six kinds of phenolcarboxylic acid derivatives, 11 kinds of polyphenol mixtures and five kinds of crude plant tannin extracts. The effects of these TRPs on freezing were examined by droplet freezing assays using various solutions containing different kinds of identified ice nucleators such as the ice nucleation bacterium (INB) Erwinia ananas, the INB Xanthomonas campestris, silver iodide and phloroglucinol as well as a solution containing only unintentionally included unidentified airborne ice nucleators. Among the 41 kinds of TRPs examined, all of the hydrolyzable tannins, catechin derivatives, polyphenol mixtures and crude plant tannin extracts as well as a few structural analogs of catechin and phenolcarboxylic acid derivatives exhibited supercooling-promoting activity (SCA) with significant differences (p>0.05) from at least one of the solutions containing different kinds of ice nucleators. It should be noted that there were no TRPs exhibiting ice nucleation-enhancing activity (INA) in all solutions containing identified ice nucleators, whereas there were many TRPs exhibiting INA with significant differences in solutions containing unidentified ice nucleators alone. An emulsion freezing assay confirmed that these TRPs did not essentially affect homogeneous ice nucleation temperatures. It is thought that not only SCA but also INA in the TRPs are produced by interactions with heterogeneous ice nucleators, not by direct interaction with water

  1. Evaluating the Liquid Liquid Phase Transition Hypothesis of Supercoooled Water

    Science.gov (United States)

    Limmer, David; Chandler, David

    2011-03-01

    To explain the anomalous behavior of supercooled water it has been conjectured that buried within an experimentally inaccessible region of liquid water's phase diagram there exists a second critical point, which is the terminus of a first order transition line between two distinct liquid phases. The so-called liquid-liquid phase transition (LLPT) has since generated much study, though to date there is no consensus on its existence. In this talk, we will discuss our efforts to systematically study the metastable phase diagram of supercooled water through computer simulation. By employing importance-sampling techniques, we have calculated free energies as a function of the density and long-range order to determine unambiguously if two distinct liquid phases exist. We will argue that, contrary to the LLPT hypothesis, the observed phenomenology can be understood as a consequence of the limit of stability of the liquid far away from coexistence. Our results suggest that homogeneous nucleation is the cause of the increased fluctuations present upon supercooling. Further we will show how this understanding can be extended to explain experimental observations of hysteresis in confined supercooled water systems.

  2. Bubble nucleation in simple and molecular liquids via the largest spherical cavity method

    International Nuclear Information System (INIS)

    Gonzalez, Miguel A.; Abascal, José L. F.; Valeriani, Chantal; Bresme, Fernando

    2015-01-01

    In this work, we propose a methodology to compute bubble nucleation free energy barriers using trajectories generated via molecular dynamics simulations. We follow the bubble nucleation process by means of a local order parameter, defined by the volume of the largest spherical cavity (LSC) formed in the nucleating trajectories. This order parameter simplifies considerably the monitoring of the nucleation events, as compared with the previous approaches which require ad hoc criteria to classify the atoms and molecules as liquid or vapor. The combination of the LSC and the mean first passage time technique can then be used to obtain the free energy curves. Upon computation of the cavity distribution function the nucleation rate and free-energy barrier can then be computed. We test our method against recent computations of bubble nucleation in simple liquids and water at negative pressures. We obtain free-energy barriers in good agreement with the previous works. The LSC method provides a versatile and computationally efficient route to estimate the volume of critical bubbles the nucleation rate and to compute bubble nucleation free-energies in both simple and molecular liquids

  3. A comparison between integral equation theory and molecular dynamics simulations of dense, flexible polymer liquids

    International Nuclear Information System (INIS)

    Curro, J.G.; Schweizer, K.S.; Grest, G.S.; Kremer, K.; Corporate Research Science Laboratory, Exxon Research and Engineering Company, Annandale, New Jersey 08801; Institut fur Festkorperforschung der Kernforschungsanlage Julich, D-5170 Julich, Federal Republic of Germany)

    1989-01-01

    Recently we (J.G.C. and K.S.S.) formulated a tractable ''reference interaction site model'' (RISM) integral equation theory of flexible polymer liquids. The purpose of this paper is to compare the results of the theory with recent molecular dynamics simulations (G.S.G. and K.K.) on dense chain liquids of degree of polymerization N=50 and 200. Specific comparisons were made between theory and simulation for the intramolecular structure factor ω(k) and the intermolecular radial distribution function g(r) in the liquid. In particular it was possible to independently test the assumptions inherent in the RISM theory and the additional ideality approximation that was made in the initial application of the theory. This comparison was accomplished by calculating the intermolecular g(r) using the simulated intramolecular structure factor, as well as, ω(k) derived from a freely jointed chain model.The RISM theory results, using the simulated ω(k), were found to be in excellent agreement, over all length scales, with the g(r) from molecular dynamics simulations. The theoretical predictions using the ''ideal'' intramolecular structure factor tended to underestimate g(r) near contact, indicating local intramolecular expansion of the chains. This local expansion can be incorporated into the theory self consistently by including the effects of the ''medium induced'' potential on the intramolecular structure

  4. Molecular reorientation of dye doped nematic liquid crystals in the laser illumination

    International Nuclear Information System (INIS)

    San, S. E.; Koeysal, O.; Ecevit, F. N.

    2002-01-01

    In this study it is investigated how dye doped nematic liquid crystals reorient under the illumination of laser beam whose wavelength is appropriate to absorbance characteristics of the doping dye. Nematic liquid crystal E7 is used with anthraquinone dye 1% wt/wt in the preparation of the sample and this material is filled in homegenously aligned measurement cell having 15 μm thickness. Mechanism of molecular reorientation includes the absorbance effects of the energy of laser by doping dye and this reorientation causes the refractive index of the material to be changed. There are potential application possibilities of such molecular reorientation based effects in nonlinear optics such as real time holography whose basis is grating diffraction that is observed and investigated in the frame of fundamentals of molecule light interaction mechanisms. Experimental analyses allowed finding characteristic values of diffraction signals depending on physical parameters of set up for a dye doped liquid crystal system and this system provided a 20 % diffraction efficiency under the optimum circumstances

  5. Molecular-dynamics study of solid–liquid interface migration in fcc metals

    International Nuclear Information System (INIS)

    Mendelev, M I; Rahman, M J; Hoyt, J J; Asta, M

    2010-01-01

    In order to establish a link between various structural and kinetic properties of metals and the crystal–melt interfacial mobility, free-solidification molecular-dynamics simulations have been performed for a total of nine embedded atom method interatomic potentials describing pure Al, Cu and Ni. To fully explore the space of materials properties three new potentials have been developed. The new potentials are based on a previous description of Al, but in each case the liquid structure, the melting point and/or the latent heat are varied considerably. The kinetic coefficient, μ, for all systems has been compared with several theoretical predictions. It is found that at temperatures close to the melting point the magnitude of μ correlates well with the value of the diffusion coefficient in the liquid

  6. Molecular differences between deuterated and protonated polystyrenes using reversed-phase high-performance liquid chromatography.

    Science.gov (United States)

    Kayillo, Sindy; Gray, Michael J; Shalliker, R Andrew; Dennis, Gary R

    2005-05-06

    Isotopic substitution is a technique used to highlight particular bonds within a molecule for kinetic, spectroscopic and structure analysis. It is presumed that although some properties such as stretching frequencies will not be the same for substituted analogues, the chemical interactions will not vary appreciably as a function of labelling. Reversed-phase liquid chromatography has been used to demonstrate that there are significant differences between the chromatographic behaviour of a sequence of deuterated and protonated oligomeric polystyrenes. Two-dimensional reversed-phase liquid chromatography was used to show that even the diasteromers of the oligomers (n = 5) have retention mechanisms that are dependent on the subtle changes to the molecular conformation and electronic structure, which are a consequence of deuteration.

  7. Use of molecular beams for the analysis of liquid and solid organic compounds

    International Nuclear Information System (INIS)

    Devienne, F.M.; Giroud, Josiane.

    1975-01-01

    The chemical composition of every solid can be determined by the M.B.S.A. method (Molecular Beam Surface Analysis). The method was used to analyze deposits on a filter paper, obtained by evaporation of a liquid solution, as well a liquid films with very low evaporation rate (dioctyl-azelate for instance). The S.C.I.C. method (Separation of Ions by Collision) was used to know exactly the composition of ions of fixed mass, separated by an electromagnet. The separated ions collide a target gas (helium or argon); apart of them are dissociated and the composition and structure of the primary ions can be deduced from the kinetic energy of the dissociated ions. Results obtained from such analysis of a thin film of baryum acetate on a platinum substrate are given [fr

  8. Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo

    International Nuclear Information System (INIS)

    Zen, Andrea; Luo, Ye; Mazzola, Guglielmo; Sorella, Sandro; Guidoni, Leonardo

    2015-01-01

    Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems

  9. Communications: On artificial frequency shifts in infrared spectra obtained from centroid molecular dynamics: Quantum liquid water

    Science.gov (United States)

    Ivanov, Sergei D.; Witt, Alexander; Shiga, Motoyuki; Marx, Dominik

    2010-01-01

    Centroid molecular dynamics (CMD) is a popular method to extract approximate quantum dynamics from path integral simulations. Very recently we have shown that CMD gas phase infrared spectra exhibit significant artificial redshifts of stretching peaks, due to the so-called "curvature problem" imprinted by the effective centroid potential. Here we provide evidence that for condensed phases, and in particular for liquid water, CMD produces pronounced artificial redshifts for high-frequency vibrations such as the OH stretching band. This peculiar behavior intrinsic to the CMD method explains part of the unexpectedly large quantum redshifts of the stretching band of liquid water compared to classical frequencies, which is improved after applying a simple and rough "harmonic curvature correction."

  10. A novel numerical model to predict the morphological behavior of magnetic liquid marbles using coarse grained molecular dynamics concepts

    Science.gov (United States)

    Polwaththe-Gallage, Hasitha-Nayanajith; Sauret, Emilie; Nguyen, Nam-Trung; Saha, Suvash C.; Gu, YuanTong

    2018-01-01

    Liquid marbles are liquid droplets coated with superhydrophobic powders whose morphology is governed by the gravitational and surface tension forces. Small liquid marbles take spherical shapes, while larger liquid marbles exhibit puddle shapes due to the dominance of gravitational forces. Liquid marbles coated with hydrophobic magnetic powders respond to an external magnetic field. This unique feature of magnetic liquid marbles is very attractive for digital microfluidics and drug delivery systems. Several experimental studies have reported the behavior of the liquid marbles. However, the complete behavior of liquid marbles under various environmental conditions is yet to be understood. Modeling techniques can be used to predict the properties and the behavior of the liquid marbles effectively and efficiently. A robust liquid marble model will inspire new experiments and provide new insights. This paper presents a novel numerical modeling technique to predict the morphology of magnetic liquid marbles based on coarse grained molecular dynamics concepts. The proposed model is employed to predict the changes in height of a magnetic liquid marble against its width and compared with the experimental data. The model predictions agree well with the experimental findings. Subsequently, the relationship between the morphology of a liquid marble with the properties of the liquid is investigated. Furthermore, the developed model is capable of simulating the reversible process of opening and closing of the magnetic liquid marble under the action of a magnetic force. The scaling analysis shows that the model predictions are consistent with the scaling laws. Finally, the proposed model is used to assess the compressibility of the liquid marbles. The proposed modeling approach has the potential to be a powerful tool to predict the behavior of magnetic liquid marbles serving as bioreactors.

  11. Water liquid-vapor interface subjected to various electric fields: A molecular dynamics study

    Science.gov (United States)

    Nikzad, Mohammadreza; Azimian, Ahmad Reza; Rezaei, Majid; Nikzad, Safoora

    2017-11-01

    Investigation of the effects of E-fields on the liquid-vapor interface is essential for the study of floating water bridge and wetting phenomena. The present study employs the molecular dynamics method to investigate the effects of parallel and perpendicular E-fields on the water liquid-vapor interface. For this purpose, density distribution, number of hydrogen bonds, molecular orientation, and surface tension are examined to gain a better understanding of the interface structure. Results indicate enhancements in parallel E-field decrease the interface width and number of hydrogen bonds, while the opposite holds true in the case of perpendicular E-fields. Moreover, perpendicular fields disturb the water structure at the interface. Given that water molecules tend to be parallel to the interface plane, it is observed that perpendicular E-fields fail to realign water molecules in the field direction while the parallel ones easily do so. It is also shown that surface tension rises with increasing strength of parallel E-fields, while it reduces in the case of perpendicular E-fields. Enhancement of surface tension in the parallel field direction demonstrates how the floating water bridge forms between the beakers. Finally, it is found that application of external E-fields to the liquid-vapor interface does not lead to uniform changes in surface tension and that the liquid-vapor interfacial tension term in Young's equation should be calculated near the triple-line of the droplet. This is attributed to the multi-directional nature of the droplet surface, indicating that no constant value can be assigned to a droplet's surface tension in the presence of large electric fields.

  12. Liquid-Phase Exfoliation of Phosphorene: Design Rules from Molecular Dynamics Simulations.

    Science.gov (United States)

    Sresht, Vishnu; Pádua, Agílio A H; Blankschtein, Daniel

    2015-08-25

    The liquid-phase exfoliation of phosphorene, the two-dimensional derivative of black phosphorus, in the solvents dimethyl sulfoxide (DMSO), dimethylformamide (DMF), isopropyl alcohol, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone is investigated using three molecular-scale "computer experiments". We modeled solvent-phosphorene interactions using an atomistic force field, based on ab initio calculations and lattice dynamics, that accurately reproduces experimental mechanical properties. We probed solvent molecule ordering at phosphorene/solvent interfaces and discovered that planar molecules such as N-methyl-2-pyrrolidone preferentially orient parallel to the interface. We subsequently measured the energy required to peel a single phosphorene monolayer from a stack of black phosphorus and analyzed the role of "wedges" of solvent molecules intercalating between phosphorene sheets in initiating exfoliation. The exfoliation efficacy of a solvent is enhanced when either molecular planarity "sharpens" this molecular wedge or strong phosphorene-solvent adhesion stabilizes the newly exposed phosphorene surfaces. Finally, we examined the colloidal stability of exfoliated flakes by simulating their aggregation and showed that dispersion is favored when the cohesive energy between the molecules in the solvent monolayer confined between the phosphorene sheets is high (as with DMSO) and is hindered when the adhesion between these molecules and phosphorene is strong; the molecular planarity in solvents like DMF enhances the cohesive energy. Our results are consistent with, and provide a molecular context for, experimental exfoliation studies of phosphorene and other layered solids, and our molecular insights into the significant role of solvent molecular geometry and ordering should complement prevalent solubility-parameter-based approaches in establishing design rules for effective nanomaterial exfoliation media.

  13. Molecular dynamics simulation of nonlinear spectroscopies of intermolecular motions in liquid water.

    Science.gov (United States)

    Yagasaki, Takuma; Saito, Shinji

    2009-09-15

    Water is the most extensively studied of liquids because of both its ubiquity and its anomalous thermodynamic and dynamic properties. The properties of water are dominated by hydrogen bonds and hydrogen bond network rearrangements. Fundamental information on the dynamics of liquid water has been provided by linear infrared (IR), Raman, and neutron-scattering experiments; molecular dynamics simulations have also provided insights. Recently developed higher-order nonlinear spectroscopies open new windows into the study of the hydrogen bond dynamics of liquid water. For example, the vibrational lifetimes of stretches and a bend, intramolecular features of water dynamics, can be accurately measured and are found to be on the femtosecond time scale at room temperature. Higher-order nonlinear spectroscopy is expressed by a multitime correlation function, whereas traditional linear spectroscopy is given by a one-time correlation function. Thus, nonlinear spectroscopy yields more detailed information on the dynamics of condensed media than linear spectroscopy. In this Account, we describe the theoretical background and methods for calculating higher order nonlinear spectroscopy; equilibrium and nonequilibrium molecular dynamics simulations, and a combination of both, are used. We also present the intermolecular dynamics of liquid water revealed by fifth-order two-dimensional (2D) Raman spectroscopy and third-order IR spectroscopy. 2D Raman spectroscopy is sensitive to couplings between modes; the calculated 2D Raman signal of liquid water shows large anharmonicity in the translational motion and strong coupling between the translational and librational motions. Third-order IR spectroscopy makes it possible to examine the time-dependent couplings. The 2D IR spectra and three-pulse photon echo peak shift show the fast frequency modulation of the librational motion. A significant effect of the translational motion on the fast frequency modulation of the librational motion is

  14. A model for self-diffusion of guanidinium-based ionic liquids: a molecular simulation study.

    Science.gov (United States)

    Klähn, Marco; Seduraman, Abirami; Wu, Ping

    2008-11-06

    We propose a novel self-diffusion model for ionic liquids on an atomic level of detail. The model is derived from molecular dynamics simulations of guanidinium-based ionic liquids (GILs) as a model case. The simulations are based on an empirical molecular mechanical force field, which has been developed in our preceding work, and it relies on the charge distribution in the actual liquid. The simulated GILs consist of acyclic and cyclic cations that were paired with nitrate and perchlorate anions. Self-diffusion coefficients are calculated at different temperatures from which diffusive activation energies between 32-40 kJ/mol are derived. Vaporization enthalpies between 174-212 kJ/mol are calculated, and their strong connection with diffusive activation energies is demonstrated. An observed formation of cavities in GILs of up to 6.5% of the total volume does not facilitate self-diffusion. Instead, the diffusion of ions is found to be determined primarily by interactions with their immediate environment via electrostatic attraction between cation hydrogen and anion oxygen atoms. The calculated average time between single diffusive transitions varies between 58-107 ps and determines the speed of diffusion, in contrast to diffusive displacement distances, which were found to be similar in all simulated GILs. All simulations indicate that ions diffuse by using a brachiation type of movement: a diffusive transition is initiated by cleaving close contacts to a coordinated counterion, after which the ion diffuses only about 2 A until new close contacts are formed with another counterion in its vicinity. The proposed diffusion model links all calculated energetic and dynamic properties of GILs consistently and explains their molecular origin. The validity of the model is confirmed by providing an explanation for the variation of measured ratios of self-diffusion coefficients of cations and paired anions over a wide range of values, encompassing various ionic liquid classes

  15. Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

    Science.gov (United States)

    Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

    2011-07-21

    In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

  16. Measurement and Correlation of the Ionic Conductivity of Ionic Liquid-Molecular Solvent Solutions

    Institute of Scientific and Technical Information of China (English)

    LI,Wen-Jing; HAN,Bu-Xing; TAO,Ran-Ting; ZHANG,Zhao-Fu; ZHANG,Jian-Ling

    2007-01-01

    The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) or 1-n-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF6]) and different molecular solvents (MSs) were measured at 298.15 K. The molar conductivity of the ionic liquids (ILs) increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.

  17. Generation of thermodynamic data for organic liquid mixtures from molecular simulations

    DEFF Research Database (Denmark)

    Christensen, Steen; Peters, Günther H.j.; Hansen, Flemming Yssing

    2007-01-01

    Fluctuation solution theory (FST) is employed to analyze results of molecular dynamics (MD) simulations of liquid mixtures. The objective is to generate parameters for macroscopic thermodynamic property models. Two benchmark systems, benzene-methyl acetate at 303.15 K and benzene-ethanol at 298.......15 K, are used. MD simulations are performed in the isobaric-isothermal ensemble (NPT) at the respective temperatures and at a pressure of 1 atm. We use the CHARMM27 force field at different mixing ratios. We sample positions to determine the binary (between the centers-of-mass of molecules of a pair...

  18. Generation of live offspring from vitrified embryos with synthetic polymers SuperCool X-1000 and SuperCool Z-1000.

    Science.gov (United States)

    Marco-Jimenez, F; Jimenez-Trigos, E; Lavara, R; Vicente, J S

    2014-01-01

    Ice growth and recrystallisation are considered important factors in determining vitrification outcomes. Synthetic polymers inhibit ice formation during cooling or warming of the vitrification process. The aim of this study was to assess the effect of adding commercially available synthetic polymers SuperCool X-1000 and SuperCool Z-1000 to vitrification media on in vivo development competence of rabbit embryos. Four hundred and thirty morphologically normal embryos recovered at 72 h of gestation were used. The vitrification media contained 20% dimethyl sulphoxide and 20% ethylene glycol, either alone or in combination with 1% of SuperCool X-1000 and 1% SuperCool. Our results show that embryos can be successfully vitrified using SuperCool X-1000 and SuperCool Z-1000 and when embryos are transferred, live offspring can be successfully produced. In conclusion, our results demonstrated that we succeeded for the first time in obtaining live offspring after vitrification of embryos using SuperCool X-1000 and SuperCool Z-1000 polymers.

  19. The molecular ordering phenomenon in dye-doped nematic liquid crystals

    International Nuclear Information System (INIS)

    Prakash Yadav, Satya; Pandey, Kamal Kumar; Kumar Misra, Abhishek; Kumar Tripathi, Pankaj; Manohar, Rajiv

    2011-01-01

    The experimental results of this work point out the role of the guest dye molecules in the molecular ordering of nematic liquid crystals. We have discussed the changes in the energies of interactions between rod-like nematic molecules and anthraquinone dye by considering the presence of steric and dipole-dipole interactions in the dye-doped system. The concentration of the dye plays an important role in the determination of molecular ordering in such dye-doped systems. Below a certain concentration of dye (known as the critical concentration), where the interaction between the dye molecules can be neglected, the addition of dye molecules introduces some disorder into the system in the form of domain formation. Above this critical concentration, this disorder is small.

  20. The molecular ordering phenomenon in dye-doped nematic liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Prakash Yadav, Satya; Pandey, Kamal Kumar; Kumar Misra, Abhishek; Kumar Tripathi, Pankaj; Manohar, Rajiv, E-mail: rajiv.manohar@gmail.com [Liquid Crystal Research Laboratory, Physics Department, University of Lucknow, Lucknow-226007 (India)

    2011-03-15

    The experimental results of this work point out the role of the guest dye molecules in the molecular ordering of nematic liquid crystals. We have discussed the changes in the energies of interactions between rod-like nematic molecules and anthraquinone dye by considering the presence of steric and dipole-dipole interactions in the dye-doped system. The concentration of the dye plays an important role in the determination of molecular ordering in such dye-doped systems. Below a certain concentration of dye (known as the critical concentration), where the interaction between the dye molecules can be neglected, the addition of dye molecules introduces some disorder into the system in the form of domain formation. Above this critical concentration, this disorder is small.

  1. Decompression-induced melting of ice IV and the liquid-liquid transition in water

    Science.gov (United States)

    Mishima, Osamu; Stanley, H. Eugene

    1998-03-01

    Although liquid water has been the focus of intensive research for over 100 years, a coherent physical picture that unifies all of the known anomalies of this liquid, is still lacking. Some of these anomalies occur in the supercooled region, and have been rationalized on the grounds of a possible retracing of the liquid-gas spinodal (metastability limit) line into the supercooled liquid region, or alternatively the presence of a line of first-order liquid-liquid phase transitions in this region which ends in a critical point,. But these ideas remain untested experimentally, in part because supercooled water can be probed only above the homogeneous nucleation temperature TH at which water spontaneously crystallizes. Here we report an experimental approach that is not restricted by the barrier imposed by TH, involving measurement of the decompression-induced melting curves of several high-pressure phases of ice in small emulsified droplets. We find that the melting curve for ice IV seems to undergo a discontinuity at precisely the location proposed for the line of liquid-liquid phase transitions. This is consistent with, but does not prove, the coexistence of two different phases of (supercooled) liquid water. From the experimental data we calculate a possible Gibbs potential surface and a corresponding equation of state for water, from the forms of which we estimate the coordinates of the liquid-liquid critical point to be at pressure Pc ~ 0.1GPa and temperature Tc ~ 220K.

  2. Designing molecular complexes using free-energy derivatives from liquid-state integral equation theory

    International Nuclear Information System (INIS)

    Mrugalla, Florian; Kast, Stefan M

    2016-01-01

    Complex formation between molecules in solution is the key process by which molecular interactions are translated into functional systems. These processes are governed by the binding or free energy of association which depends on both direct molecular interactions and the solvation contribution. A design goal frequently addressed in pharmaceutical sciences is the optimization of chemical properties of the complex partners in the sense of minimizing their binding free energy with respect to a change in chemical structure. Here, we demonstrate that liquid-state theory in the form of the solute–solute equation of the reference interaction site model provides all necessary information for such a task with high efficiency. In particular, computing derivatives of the potential of mean force (PMF), which defines the free-energy surface of complex formation, with respect to potential parameters can be viewed as a means to define a direction in chemical space toward better binders. We illustrate the methodology in the benchmark case of alkali ion binding to the crown ether 18-crown-6 in aqueous solution. In order to examine the validity of the underlying solute–solute theory, we first compare PMFs computed by different approaches, including explicit free-energy molecular dynamics simulations as a reference. Predictions of an optimally binding ion radius based on free-energy derivatives are then shown to yield consistent results for different ion parameter sets and to compare well with earlier, orders-of-magnitude more costly explicit simulation results. This proof-of-principle study, therefore, demonstrates the potential of liquid-state theory for molecular design problems. (paper)

  3. A comparative study of ibuprofen and ketoprofen glass-forming liquids by molecular dynamics simulations

    Science.gov (United States)

    Ottou Abe, M. T.; Correia, N. T.; Ndjaka, J. M. B.; Affouard, F.

    2015-10-01

    In this paper, structural and dynamical properties of ibuprofen and ketoprofen glass-forming liquids have been investigated by means of molecular dynamics simulations. Molecular mobility of both materials is analyzed with respect to the different inter-molecular linear/cyclic hydrogen bonding associations. For ibuprofen, the dominant organization is found to be composed of small hydrogen bonding aggregates corresponding to cyclic dimers through the carboxyl group. For ketoprofen, the propensity of cyclic dimers is significantly reduced by the formation of hydrogen bonds with the ketone oxygen of the molecule altering the hydrogen bond (HB) associating structures that can be formed and thus molecular dynamics. The issue of the presence/absence of the peculiar low frequency Debye-type process in dielectric relaxation spectroscopy (DRS) data in these materials is addressed. Results obtained from simulations confirm that the Debye process originates from the internal cis-trans conversion of the —COOH carboxyl group. It is shown that the specific intermolecular HB structures associated to a given profen control the main dynamical features of this conversion, in particular its separation from the α-process, which make it detectable or not from DRS. For ibuprofen, the possible role of the —CCCO torsion motion, more "local" than the —COOH motion since it is less influenced by the intermolecular HBs, is suggested in the microscopic origin of the quite intense secondary γ-relaxation process detected from DRS.

  4. Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations.

    Science.gov (United States)

    Sosso, Gabriele C; Chen, Ji; Cox, Stephen J; Fitzner, Martin; Pedevilla, Philipp; Zen, Andrea; Michaelides, Angelos

    2016-06-22

    The nucleation of crystals in liquids is one of nature's most ubiquitous phenomena, playing an important role in areas such as climate change and the production of drugs. As the early stages of nucleation involve exceedingly small time and length scales, atomistic computer simulations can provide unique insights into the microscopic aspects of crystallization. In this review, we take stock of the numerous molecular dynamics simulations that, in the past few decades, have unraveled crucial aspects of crystal nucleation in liquids. We put into context the theoretical framework of classical nucleation theory and the state-of-the-art computational methods by reviewing simulations of such processes as ice nucleation and the crystallization of molecules in solutions. We shall see that molecular dynamics simulations have provided key insights into diverse nucleation scenarios, ranging from colloidal particles to natural gas hydrates, and that, as a result, the general applicability of classical nucleation theory has been repeatedly called into question. We have attempted to identify the most pressing open questions in the field. We believe that, by improving (i) existing interatomic potentials and (ii) currently available enhanced sampling methods, the community can move toward accurate investigations of realistic systems of practical interest, thus bringing simulations a step closer to experiments.

  5. On the application of accelerated molecular dynamics to liquid water simulations.

    Science.gov (United States)

    de Oliveira, César Augusto F; Hamelberg, Donald; McCammon, J Andrew

    2006-11-16

    Our group recently proposed a robust bias potential function that can be used in an efficient all-atom accelerated molecular dynamics (MD) approach to simulate the transition of high energy barriers without any advance knowledge of the potential-energy landscape. The main idea is to modify the potential-energy surface by adding a bias, or boost, potential in regions close to the local minima, such that all transitions rates are increased. By applying the accelerated MD simulation method to liquid water, we observed that this new simulation technique accelerates the molecular motion without losing its microscopic structure and equilibrium properties. Our results showed that the application of a small boost energy on the potential-energy surface significantly reduces the statistical inefficiency of the simulation while keeping all the other calculated properties unchanged. On the other hand, although aggressive acceleration of the dynamics simulation increases the self-diffusion coefficient of water molecules greatly and dramatically reduces the correlation time of the simulation, configurations representative of the true structure of liquid water are poorly sampled. Our results also showed the strength and robustness of this simulation technique, which confirm this approach as a very useful and promising tool to extend the time scale of the all-atom simulations of biological system with explicit solvent models. However, we should keep in mind that there is a compromise between the strength of the boost applied in the simulation and the reproduction of the ensemble average properties.

  6. Field-dependent molecular ionization and excitation energies: Implications for electrically insulating liquids

    Directory of Open Access Journals (Sweden)

    N. Davari

    2014-03-01

    Full Text Available The molecular ionization potential has a relatively strong electric-field dependence as compared to the excitation energies which has implications for electrical insulation since the excited states work as an energy sink emitting light in the UV/VIS region. At some threshold field, all the excited states of the molecule have vanished and the molecule is a two-state system with the ground state and the ionized state, which has been hypothesized as a possible origin of different streamer propagation modes. Constrained density-functional theory is used to calculate the field-dependent ionization potential of different types of molecules relevant for electrically insulating liquids. The low singlet-singlet excitation energies of each molecule have also been calculated using time-dependent density functional theory. It is shown that low-energy singlet-singlet excitation of the type n → π* (lone pair to unoccupied π* orbital has the ability to survive at higher fields. This type of excitation can for example be found in esters, diketones and many color dyes. For alkanes (as for example n-tridecane and cyclohexane on the other hand, all the excited states, in particular the σ → σ* excitations vanish in electric fields higher than 10 MV/cm. Further implications for the design of electrically insulating dielectric liquids based on the molecular ionization potential and excitation energies are discussed.

  7. Equations of states for an ionic liquid under high pressure: A molecular dynamics simulation study

    International Nuclear Information System (INIS)

    Ribeiro, Mauro C.C.; Pádua, Agílio A.H.; Gomes, Margarida F.C.

    2014-01-01

    Highlights: • We compare different equation of states, EoS, for an ionic liquid under high pressure. • Molecular dynamics, MD, simulations have been used to evaluate the best EoS. • MD simulations show that a group contribution model can be extrapolated to P ∼ 1.0 GPa. • A perturbed hard-sphere EoS also fits the densities calculated by MD simulations. - Abstract: The high-pressure dependence of density given by empirical equation of states (EoS) for the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (or triflate), [C 4 C 1 im][TfO], is compared with results obtained by molecular dynamics (MD) simulations. Two EoS proposed for [C 4 C 1 im][TfO] in the pressure range of tens of MPa, which give very different densities when extrapolated to pressures beyond the original experiments, are compared with a group contribution model (GCM). The MD simulations provide support that one of the empirical EoS and the GCM is valid in the pressure range of hundreds of MPa. As an alternative to these EoS that are based on modified Tait equations, it is shown that a perturbed hard-sphere EoS based on the Carnahan–Starling–van der Waals equation also fits the densities calculated by MD simulations of [C 4 C 1 im][TfO] up to ∼1.0 GPa

  8. Absorption Refrigeration Cycles with Ammonia-Ionic Liquid Working Pairs Studied by Molecular Simulation.

    Science.gov (United States)

    Becker, Tim M; Wang, Meng; Kabra, Abhishek; Jamali, Seyed Hossein; Ramdin, Mahinder; Dubbeldam, David; Infante Ferreira, Carlos A; Vlugt, Thijs J H

    2018-04-18

    For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf 2 N], and [emim][SCN]. As refrigerant NH 3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance.

  9. Absorption Refrigeration Cycles with Ammonia–Ionic Liquid Working Pairs Studied by Molecular Simulation

    Science.gov (United States)

    2018-01-01

    For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf2N], and [emim][SCN]. As refrigerant NH3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance. PMID:29749996

  10. Effects of poly-vinyl alcohol on supercooling phenomena of water

    Energy Technology Data Exchange (ETDEWEB)

    Kumano, Hiroyuki; Hirata, Tetsuo; Kudoh, Tomoya [Department of Mechanical Systems Engineering, Shinshu University, 4-17-1, Wakasato, Nagano City, 380-8553 (Japan)

    2009-05-15

    The effects of a polymer additive on the supercooling of water were investigated experimentally. Poly-vinyl alcohols (PVAs) were used as the additives, and samples were prepared by dissolving the PVA in water. Since the characteristics of PVA are decided by its degrees of polymerization and saponification, these were varied along with the concentration as the experimental parameters. Moreover, the effect of purity of the water was also considered. Each sample was cooled and the temperature at the instant when ice appeared was measured. Since the freezing of supercooled water is a statistical phenomenon, many experiments were carried out and the average degree of supercooling was obtained. It was found that PVA affects the nucleation of ice in supercooled water and the degree of supercooling increases with the addition of PVA even for water with low purity. The average degree of supercooling increases with an increase in the degree of saponification of PVA. (author)

  11. On the quantification of the dissolved hydroxyl radicals in the plasma-liquid system using the molecular probe method

    Science.gov (United States)

    Ma, Yupengxue; Gong, Xinning; He, Bangbang; Li, Xiaofei; Cao, Dianyu; Li, Junshuai; Xiong, Qing; Chen, Qiang; Chen, Bing Hui; Huo Liu, Qing

    2018-04-01

    Hydroxyl (OH) radical is one of the most important reactive species produced by plasma-liquid interactions, and the OH in liquid phase (dissolved OH radical, OHdis) takes effect in many plasma-based applications due to its high reactivity. Therefore, the quantification of the OHdis in a plasma-liquid system is of great importance, and a molecular probe method usually used for the OHdis detection might be applied. Herein, we investigate the validity of using the molecular probe method to estimate the [OHdis] in the plasma-liquid system. Dimethyl sulfoxide is used as the molecular probe to estimate the [OHdis] in an air plasma-liquid system, and usually the estimation of [OHdis] is deduced by quantifying the OHdis-induced derivative, the formaldehyde (HCHO). The analysis indicates that the true concentration of the OHdis should be estimated from the sum of three terms: the formed HCHO, the existing OH scavengers, and the H2O2 formed from the OHdis. The results show that the measured [HCHO] needs to be corrected since the HCHO consumption is not negligible in the plasma-liquid system. We conclude from the results and the analysis that the molecular probe method generally underestimates the [OHdis] in the plasma-liquid system. If one wants to obtain the true concentration of the OHdis in the plasma-liquid system, one needs to know the consumption behavior of the OHdis-induced derivatives, the information of the OH scavengers (such as hydrated electron, atomic hydrogen besides the molecular probe), and also the knowledge of the H2O2 formed from the OHdis.

  12. Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin

    OpenAIRE

    Kim, Yiseul; Hong, Geun-Pyo

    2016-01-01

    This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4? for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4?. Despite that SSF was conducted with the ...

  13. Is high pressure liquid chromatography an effective screening tool for characterization of molecular defects in hemoglobinopathies?

    Directory of Open Access Journals (Sweden)

    Nikhil Moorchung

    2013-01-01

    Full Text Available Introduction: Hemoglobinopathies constitute entities that are generated by either abnormal hemoglobin or thalassemias. high pressure liquid chromatography (HPLC is one of the best methods for screening and detection of various hemoglobinopathies but it has intrinsic interpretive problems. The study was designed to evaluate the different mutations seen in cases of hemoglobinopathies and compare the same with screening tests. Materials and Methods: 68 patients of hemoglobinopathies were screened by HPLC. Mutation studies in the beta globin gene was performed using the polymerase chain reaction (PCR-based allele-specific Amplification Refractory Mutation System (ARMS. Molecular analysis for the sickle cell mutation was done by standard methods. Results: The IVS 1/5 mutation was the commonest mutation seen and it was seen in 26 (38.23% of the cases. This was followed by the IVS 1/1, codon 41/42, codon 8/9, del 22 mutation, codon 15 mutation and the -619 bp deletion. No mutation was seen in eight cases. There was a 100% concordance between the sickle cell trait as diagnosed by HPLC and genetic testing. Discussion and Conclusion: Our study underlies the importance of molecular testing in all cases of hemoglobinopathies. Although HPLC is a useful screening tool, molecular testing is very useful in accurately diagnosing the mutations. Molecular testing is especially applicable in cases with an abnormal hemoglobin (HbD, HbE and HbS because there may be a concomitant inheritance of a beta thalassemia mutation. Molecular testing is the gold standard when it comes to the diagnosis of hemoglobinopathies.

  14. Infrared and Raman Spectroscopy of Liquid Water through "First-Principles" Many-Body Molecular Dynamics.

    Science.gov (United States)

    Medders, Gregory R; Paesani, Francesco

    2015-03-10

    Vibrational spectroscopy is a powerful technique to probe the structure and dynamics of water. However, deriving an unambiguous molecular-level interpretation of the experimental spectral features remains a challenge due to the complexity of the underlying hydrogen-bonding network. In this contribution, we present an integrated theoretical and computational framework (named many-body molecular dynamics or MB-MD) that, by systematically removing uncertainties associated with existing approaches, enables a rigorous modeling of vibrational spectra of water from quantum dynamical simulations. Specifically, we extend approaches used to model the many-body expansion of interaction energies to develop many-body representations of the dipole moment and polarizability of water. The combination of these "first-principles" representations with centroid molecular dynamics simulations enables the simulation of infrared and Raman spectra of liquid water under ambient conditions that, without relying on any ad hoc parameters, are in good agreement with the corresponding experimental results. Importantly, since the many-body energy, dipole, and polarizability surfaces employed in the simulations are derived independently from accurate fits to correlated electronic structure data, MB-MD allows for a systematic analysis of the calculated spectra in terms of both electronic and dynamical contributions. The present analysis suggests that, while MB-MD correctly reproduces both the shifts and the shapes of the main spectroscopic features, an improved description of quantum dynamical effects possibly combined with a dissociable water potential may be necessary for a quantitative representation of the OH stretch band.

  15. Roles of water in protein structure and function studied by molecular liquid theory.

    Science.gov (United States)

    Imai, Takashi

    2009-01-01

    The roles of water in the structure and function of proteins have not been completely elucidated. Although molecular simulation has been widely used for the investigation of protein structure and function, it is not always useful for elucidating the roles of water because the effect of water ranges from atomic to thermodynamic level. The three-dimensional reference interaction site model (3D-RISM) theory, which is a statistical-mechanical theory of molecular liquids, can yield the solvation structure at the atomic level and calculate the thermodynamic quantities from the intermolecular potentials. In the last few years, the author and coworkers have succeeded in applying the 3D-RISM theory to protein aqueous solution systems and demonstrated that the theory is useful for investigating the roles of water. This article reviews some of the recent applications and findings, which are concerned with molecular recognition by protein, protein folding, and the partial molar volume of protein which is related to the pressure effect on protein.

  16. Thermophysical Properties of Homologous Tetracyanoborate-Based Ionic Liquids Using Experiments and Molecular Dynamics Simulations.

    Science.gov (United States)

    Koller, Thomas M; Ramos, Javier; Schulz, Peter S; Economou, Ioannis G; Rausch, Michael H; Fröba, Andreas P

    2017-04-27

    Thermophysical properties of low-viscosity ionic liquids (ILs) based on the tetracyanoborate ([B(CN) 4 ] - ) anion carrying a homologous series of 1-alkyl-3-methylimidazolium ([AMIM] + ) cations [EMIM] + (ethyl), [BMIM] + (butyl), [HMIM] + (hexyl), [OMIM] + (octyl), and [DMIM] + (decyl) were investigated by experimental methods and molecular dynamics (MD) simulations at atmospheric pressure and various temperatures. Spectroscopic methods based on nuclear magnetic resonance and surface light scattering were applied to measure the ion self-diffusion coefficients and dynamic viscosity, respectively. In terms of MD simulations, a nonpolarizable molecular model for [EMIM][B(CN) 4 ] developed by optimization to experimental data was transferred to the other homologous ILs. For the appropriate description of the inter- and intramolecular interactions, precise and approximate force fields (FFs) were tested regarding their transferability within the homologous IL series, aiming at reducing the computational effort in molecular simulations. It is shown that at comparable simulated and experimental densities, the calculated and measured data for viscosity and self-diffusion coefficients of the ILs agree well mostly within combined uncertainties, but deviate stronger for longer-chained ILs using an overly coarse FF model. For the [B(CN) 4 ] - -based ILs studied, a comparison with literature data, the influence of varying alkyl chain length in the cation on their structural and thermophysical properties, and a correlation between self-diffusivity and viscosity are discussed.

  17. Correlation of the vapor pressure isotope effect with molecular force fields in the liquid state

    International Nuclear Information System (INIS)

    Pollin, J.S.; Ishida, T.

    1976-07-01

    The present work is concerned with the development and application of a new model for condensed phase interactions with which the vapor pressure isotope effect (vpie) may be related to molecular forces and structure. The model considers the condensed phase as being represented by a cluster of regularly arranged molecules consisting of a central molecule and a variable number of molecules in the first coordination shell. The methods of normal coordinate analysis are used to determine the modes of vibration of the condensed phase cluster from which, in turn, the isotopic reduced partition function can be calculated. Using the medium cluster model, the observed vpie for a series of methane isotopes has been successfully reproduced with better agreement with experiment than has been possible using the simple cell model. We conclude, however, that insofar as the medium cluster model provides a reasonable picture of the liquid state, the vpie is not sufficiently sensitive to molecular orientation to permit an experimental determination of intermolecular configuration in the condensed phase through measurement of isotopic pressure ratios. The virtual independence of vapor pressure isotope effects on molecular orientation at large cluster sizes is a demonstration of the general acceptability of the cell model assumptions for vpie calculations

  18. Post-irradiation chemical reactions during devitrification of molecular matrices (review)

    International Nuclear Information System (INIS)

    Barkalov, I.M.; Kiryukhin, D.P.

    1993-01-01

    At temperatures above the melting point (mp) a material is in a thermodynamic equilibrium state, in which any thermodynamic function of state (specific volume, enthalpy, and entrophy) is governed unambiguously by the temperature, pressure, etc. At temperatures below the mp, the material is converted to another equilibrium state, i.e., a crystal. However, during rapid cooling, a state of a nonequilibrium supercooled liquid can be obtained. Further cooling of this state below the glass-transition temperature, T g1 , leads to the additional formation of a nonequilibrium solid amorphous state, often simply called glass. In the vitreous state, species are capable of only vibrational and small-scale rotational motions. The translational mobility that is characteristic of the liquid state is completely lost. Very important for what follows is the fact that the transition from a supercooled liquid to the vitreous state or the reverse transition (devitrification) is accompanied by a sharp change of properties: the viscosity changes by 10-15 orders of magnitude, the modulus of elasticity changes 10-1000 fold, the coefficient of thermal expansion changes 10-100 fold, etc. Most impressive is the gigantic viscosity jump in the narrow temperature-dependent glass-transition region. This means that the molecular mobility governing the chemical-transformation dynamics undergoes a sharp change in this region. The nature of the chemical process during passage through the glass-softening region should change because of a sharp change of the mobility of the reactants, with a huge change of molecular mobility being attained by a temperature change of only a few degrees. During radiolysis of vitreous matrices, active species of radical and ionic nature are formed. This review discusses the recombination reactions of radiolysis products during heating to the supercooled state

  19. Evolution of local atomic structure during solidification of Al2Au liquid: An ab initio study

    International Nuclear Information System (INIS)

    Xiong, L.H.; Lou, H.B.; Wang, X.D.; Debela, T.T.; Cao, Q.P.; Zhang, D.X.; Wang, S.Y.; Wang, C.Z.; Jiang, J.Z.

    2014-01-01

    The local atomic structure evolution in Al 2 Au alloy during solidification from 2000 K to 400 K was studied by ab initio molecular dynamics simulations and analyzed using the structure factor, pair correlation functions, bond angle distributions, the Honeycutt–Anderson (HA) index and Voronoi tessellation methods. It was found that the icosahedral-like clusters are negligible in the Al 2 Au stable liquid and supercooled liquid states, and the most abundant clusters are those having HA indices of 131 and 120 or Voronoi indices of 〈0, 4, 4, 0〉, 〈0, 3, 6, 0〉 and 〈0, 4, 4, 2〉 with coordination numbers of 8, 9 and 10, respectively. These clusters are similar to the local atomic structures in the CaF 2 -type Al 2 Au crystal, revealing the existence of structure heredity between liquid and crystalline phase in Al 2 Au alloy

  20. Evolution of local atomic structure during solidification of Al2Au liquid: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, L H; Lou, H B; Wang, X D; Debela, T T; Cao, Q P; Zhang, D X; Wang, S Y; Wang, C Z; Jiang, J Z

    2014-04-01

    The local atomic structure evolution in Al2Au alloy during solidification from 2000 K to 400 K was studied by ab initio molecular dynamics simulations and analyzed using the structure factor, pair correlation functions, bond angle distributions, the Honeycutt-Anderson (HA) index and Voronoi tessellation methods. It was found that the icosahedral-like clusters are negligible in the Al2Au stable liquid and supercooled liquid states, and the most abundant clusters are those having HA indices of 131 and 120 or Voronoi indices of < 0,4,4,0 >, < 0,3, 6,0 > and < 0,4,4,2 > with coordination numbers of 8, 9 and 10, respectively. These clusters are similar to the local atomic structures in the CaF2-type Al2Au crystal, revealing the existence of structure heredity between liquid and crystalline phase in Al2Au alloy. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  1. Kinetics and Thermodynamics of Flexographic-plate Polymer Interaction With Low-molecular Liquids

    Directory of Open Access Journals (Sweden)

    Akaky Dzhvarsheyshvili

    2007-11-01

    Full Text Available Flexographic printing plates contact solvents in the process of their production and operation: washing solvents and printing paint components. As a results of such contact plates swell. Swelling changes polymers’ elastic properties of which the plate is made, changes the scan point sizes that, in the final analysis, affects the printing product quality. The kinetics of swelling flexographic plate polymer interaction with low-molecular liquids used in the process of plate production and operation was studied. Constants of speed, parameters Flory - Huggins, diffusion coefficient D for each solvent was determined. The changes of the basic thermodynamic functions ΔG, ΔS, ΔH of swelling, are calculated. The received data allow to choose the optimum solvents for processes of polygraphic technology.

  2. Immobilization induced molecular compression of ionic liquid in ordered mesoporous matrix

    Science.gov (United States)

    Tripathi, Alok Kumar; Singh, Rajendra Kumar

    2018-02-01

    In this work, ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ([EMIM][FSI]) has been immobilized into ordered mesoporous silica MCM-41 by a physical imbibition process. Transmission electron microscopy confirms the filling of mesopores of MCM-41. The effect of IL content in MCM-41 was probed in terms of thermal stability, chemical interactions, and dielectric properties. N2-sorption results indicate the compression of the IL in the nanopores of MCM-41, which contributes to an increase of the melting point probed by differential scanning calorimetry. The quantum chemical calculations confirmed that the ion-ion interaction in ion-pairs of IL were preferred over the hydrogen bonding interaction in the presence of SiO2 molecules, and these interactions probably compress the molecular size in the nanopores of MCM-41. Strong interactions between IL and porous MCM-41 were suggested as the mechanism of this immobilization, which was characterized by FTIR and dielectric spectroscopy.

  3. Molecular design of high performance zwitterionic liquids for enhanced heavy-oil recovery processes.

    Science.gov (United States)

    Martínez-Magadán, J M; Cartas-Rosado, A R; Oviedo-Roa, R; Cisneros-Dévora, R; Pons-Jiménez, M; Hernández-Altamirano, R; Zamudio-Rivera, L S

    2018-03-01

    Branched gemini zwitterionic liquids, which contain two zwitterionic moieties of linked quaternary-ammonium and carboxylate groups, are proposed as chemicals to be applied in the Enhanced Oil Recovery (EOR) from fractured carbonate reservoirs. The zwitterionic moieties are bridged between them through an alkyl chain containing 12 ether groups, and each zwitterionic moiety has attached a long alkyl tail including a CC double bond. A theoretical molecular mechanism over which EOR could rest, consisting on both the disaggregation of heavy oil and the reservoir-rock wettability alteration, was suggested. Results show that chemicals can both reduce the viscosity and remove heavy-oil molecules from the rock surface. Copyright © 2018. Published by Elsevier Inc.

  4. Thermophysical properties of liquid Ni around the melting temperature from molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Rozas, R. E. [Institut für Theoretische Physik II: Soft Matter, Heinrich Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf (Germany); Department of Physics, University of Bío-Bío, Av. Collao 1202, P.O. Box 5C, Concepción (Chile); Demiraǧ, A. D.; Horbach, J. [Institut für Theoretische Physik II: Soft Matter, Heinrich Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf (Germany); Toledo, P. G. [Chemical Engineering Department and Surface Analysis Laboratory (ASIF), University of Concepción, P.O. Box 160-C, Correo 3, Concepción (Chile)

    2016-08-14

    Thermophysical properties of liquid nickel (Ni) around the melting temperature are investigated by means of classical molecular dynamics (MD) simulation, using three different embedded atom method potentials to model the interactions between the Ni atoms. Melting temperature, enthalpy, static structure factor, self-diffusion coefficient, shear viscosity, and thermal diffusivity are compared to recent experimental results. Using ab initio MD simulation, we also determine the static structure factor and the mean-squared displacement at the experimental melting point. For most of the properties, excellent agreement is found between experiment and simulation, provided the comparison relative to the corresponding melting temperature. We discuss the validity of the Hansen-Verlet criterion for the static structure factor as well as the Stokes-Einstein relation between self-diffusion coefficient and shear viscosity. The thermal diffusivity is extracted from the autocorrelation function of a wavenumber-dependent temperature fluctuation variable.

  5. Detailed molecular characterization of castor oil ethoxylates by liquid chromatography multistage mass spectrometry.

    Science.gov (United States)

    Nasioudis, Andreas; van Velde, Jan W; Heeren, Ron M A; van den Brink, Oscar F

    2011-10-07

    The molecular characterization of castor oil ethoxylates (CASEOs) was studied by reverse-phase liquid chromatography (RPLC) mass spectrometry (MS) and multistage mass spectrometry (MS(n)). The developed RPLC method allowed the separation of the various CASEO components, and especially, the baseline separation of multiple nominal isobars (same nominal mass) and isomers (same exact mass). MS and MS(n) were used for the determination and structure elucidation of various structures and for the discrimination of the isobars and isomers. Different ionization techniques and adduct ions were also tested for optimization of the MS detection and the MS(n) fragmentation. A unique fragmentation pathway of ricinoleic acid is proposed, which can be used as a marker of the polymerization process and the topology of ethoxylation in the CASEO. In addition, characteristic neutral losses of ricinoleic acid reveal its (terminal or internal) position in the molecule. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Synthesis and Self-Assembly of Chiral Cylindrical Molecular Complexes: Functional Heterogeneous Liquid-Solid Materials Formed by Helicene Oligomers

    Directory of Open Access Journals (Sweden)

    Nozomi Saito

    2018-01-01

    Full Text Available Chiral cylindrical molecular complexes of homo- and hetero-double-helices derived from helicene oligomers self-assemble in solution, providing functional heterogeneous liquid-solid materials. Gels and liotropic liquid crystals are formed by fibril self-assembly in solution; molecular monolayers and fibril films are formed by self-assembly on solid surfaces; gels containing gold nanoparticles emit light; silica nanoparticles aggregate and adsorb double-helices. Notable dynamics appears during self-assembly, including multistep self-assembly, solid surface catalyzed double-helix formation, sigmoidal and stairwise kinetics, molecular recognition of nanoparticles, discontinuous self-assembly, materials clocking, chiral symmetry breaking and homogeneous-heterogeneous transitions. These phenomena are derived from strong intercomplex interactions of chiral cylindrical molecular complexes.

  7. Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes.

    Science.gov (United States)

    Abedini, Asghar; Crabtree, Ellis; Bara, Jason E; Turner, C Heath

    2017-10-24

    Polyimides are at the forefront of advanced membrane materials for CO 2 capture and gas-purification processes. Recently, ionic polyimides (i-PIs) have been reported as a new class of condensation polymers that combine structural components of both ionic liquids (ILs) and polyimides through covalent linkages. In this study, we report CO 2 and CH 4 adsorption and structural analyses of an i-PI and an i-PI + IL composite containing [C 4 mim][Tf 2 N]. The combination of molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations is used to compute the gas solubility and the adsorption performance with respect to the density, fractional free volume (FFV), and surface area of the materials. Our results highlight the polymer relaxation process and its correlation to the gas solubility. In particular, the surface area can provide meaningful guidance with respect to the gas solubility, and it tends to be a more sensitive indicator of the adsorption behavior versus only considering the system density and FFV. For instance, as the polymer continues to relax, the density, FFV, and pore-size distribution remain constant while the surface area can continue to increase, enabling more adsorption. Structural analyses are also conducted to identify the nature of the gas adsorption once the ionic liquid is added to the polymer. The presence of the IL significantly displaces the CO 2 molecules from the ligand nitrogen sites in the neat i-PI to the imidazolium rings in the i-PI + IL composite. However, the CH 4 molecules move from the imidazolium ring sites in the neat i-PI to the ligand nitrogen atoms in the i-PI + IL composite. These molecular details can provide critical information for the experimental design of highly selective i-PI materials as well as provide additional guidance for the interpretation of the simulated adsorption systems.

  8. Effect of annealing conditions on the molecular properties and wetting of viscoelastic bitumen substrates by liquids

    Directory of Open Access Journals (Sweden)

    Salomé dos Santos

    2017-01-01

    Full Text Available Typically, in the production of asphalt concrete, bitumen and mineral aggregates are heated and mixed at temperatures above 100 °C. After the mixing process bitumen ideally coats the mineral aggregates and remains in the form of thin films. Because bitumen is highly temperature sensitive, the study of its properties in terms of chemistry, microstructure and rheology as a function of different annealing conditions is very relevant. The resultant molecular properties have a direct correlation to bitumen macroscopic response to liquids such as water, which is of extreme relevance to the understanding of the detrimental effect of water on asphalt pavements. The wetting characteristics play a crucial role on the extension of detachment of bitumen from the mineral aggregates when asphalt is exposed to wet conditions. Therefore, in this work, the effect of the annealing temperature and cooling history on the chemistry, microstructure and wetting of bitumen films was studied. Crystalline microstructures were identified in bulk and on the surface of the bitumen films. Larger crystals presenting higher crystallinity degree were identified when the annealed bitumen films were cooled slowly. Moreover, higher annealing temperatures increased the oxidation level. The change of the rheological properties due to the alterations of the annealing conditions produced changes in the wetting characteristics. For instance, the advancing motion of a liquid drop on the viscoelastic bitumen substrate presented an intermittent behaviour due to the deformation of bitumen at the liquid-bitumen-air contact line. Consequently, changes in the contact angles were also observed. Keywords: Bitumen, Crystallization, Oxidation, Advancing contact angle, Wetting

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

    Science.gov (United States)

    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.

  10. Molecular dynamics study of room temperature ionic liquids with water at mica surface

    Directory of Open Access Journals (Sweden)

    Huanhuan Zhang

    2018-04-01

    Full Text Available Water in room temperature ionic liquids (RTILs could impose significant effects on their interfacial properties at a charged surface. Although the interfaces between RTILs and mica surfaces exhibit rich microstructure, the influence of water content on such interfaces is little understood, in particular, considering the fact that RTILs are always associated with water due to their hygroscopicity. In this work, we studied how different types of RTILs and different amounts of water molecules affect the RTIL-mica interfaces, especially the water distribution at mica surfaces, using molecular dynamics (MD simulation. MD results showed that (1 there is more water and a thicker water layer adsorbed on the mica surface as the water content increases, and correspondingly the average location of K+ ions is farther from mica surface; (2 more water accumulated at the interface with the hydrophobic [Emim][TFSI] than in case of the hydrophilic [Emim][BF4] due to the respective RTIL hydrophobicity and ion size. A similar trend was also observed in the hydrogen bonds formed between water molecules. Moreover, the 2D number density map of adsorbed water revealed that the high-density areas of water seem to be related to K+ ions and silicon/aluminum atoms on mica surface. These results are of great importance to understand the effects of hydrophobicity/hydrophicility of RTIL and water on the interfacial microstructure at electrified surfaces. Keywords: Room temperature ionic liquids, Hydrophobicity/hydrophicility, Water content, Electrical double layer, Mica surface

  11. Properties of liquid clusters in large-scale molecular dynamics nucleation simulations

    International Nuclear Information System (INIS)

    Angélil, Raymond; Diemand, Jürg; Tanaka, Kyoko K.; Tanaka, Hidekazu

    2014-01-01

    We have performed large-scale Lennard-Jones molecular dynamics simulations of homogeneous vapor-to-liquid nucleation, with 10 9 atoms. This large number allows us to resolve extremely low nucleation rates, and also provides excellent statistics for cluster properties over a wide range of cluster sizes. The nucleation rates, cluster growth rates, and size distributions are presented in Diemand et al. [J. Chem. Phys. 139, 74309 (2013)], while this paper analyses the properties of the clusters. We explore the cluster temperatures, density profiles, potential energies, and shapes. A thorough understanding of the properties of the clusters is crucial to the formulation of nucleation models. Significant latent heat is retained by stable clusters, by as much as ΔkT = 0.1ε for clusters with size i = 100. We find that the clusters deviate remarkably from spherical—with ellipsoidal axis ratios for critical cluster sizes typically within b/c = 0.7 ± 0.05 and a/c = 0.5 ± 0.05. We examine cluster spin angular momentum, and find that it plays a negligible role in the cluster dynamics. The interfaces of large, stable clusters are thinner than planar equilibrium interfaces by 10%−30%. At the critical cluster size, the cluster central densities are between 5% and 30% lower than the bulk liquid expectations. These lower densities imply larger-than-expected surface areas, which increase the energy cost to form a surface, which lowers nucleation rates

  12. Probing spatial locality in ionic liquids with the grand canonical adaptive resolution molecular dynamics technique

    Science.gov (United States)

    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.

  13. Interfaces of dicationic ionic liquids and graphene: a molecular dynamics simulation study

    International Nuclear Information System (INIS)

    Li, Song; Feng, Guang; Cummings, Peter T

    2014-01-01

    Molecular dynamics simulations were performed to investigate the interfacial structure and capacitance of electrical double layers (EDLs) in dicationic ionic liquids (DILs) 1-alkyl-3-dimethylimidazolium tetrafluoroborate [C n (mim) 2 ](BF 4 ) 2 (n = 3, 6, 9), with respect to a baseline of a monocationic ionic liquid [C 3 mim][BF 4 ], near planar carbon electrodes consisting of graphene sheets. The simulation results show that an adsorbed layer with double peaks is exclusively found for [C 3 (mim) 2 ](BF 4 ) 2 , while a single peak of the other three cations is observed at the neutral electrode, due to the difference in ion–wall interaction and cation–anion association. As the electrode becomes negatively charged, the second peak of [C 3 (mim) 2 ] 2+ is dramatically reduced, whereas those of [C 6 (mim) 2 ] 2+ and [C 9 (mim) 2 ] 2+ become non-trivial. The capacitance–potential curve of EDLs in DILs manifests a transition from camel shape to bell shape as the cation chain length increases, which is attributed to the enlargement of ion adsorption (per unit charge) on the electrode and the decrease of attractive interaction between ions. (paper)

  14. A molecular dynamics study of liquid layering and thermal conductivity enhancement in nanoparticle suspensions

    Science.gov (United States)

    Paul, J.; Madhu, A. K.; Jayadeep, U. B.; Sobhan, C. B.; Peterson, G. P.

    2018-03-01

    Liquid layering is considered to be one of the factors contributing to the often anomalous enhancement in thermal conductivity of nanoparticle suspensions. The extent of this layering was found to be significant at lower particle sizes, as reported in an earlier work by the authors. In continuation to that work, an investigation was conducted to better understand the fundamental parameters impacting the reported anomalous enhancement in thermal conductivity of nanoparticle suspensions (nanofluids), utilizing equilibrium molecular dynamics simulations in a copper-argon system. Nanofluids containing nanoparticles of size less than 6 nm were investigated and studied analytically. The heat current auto-correlation function in the Green-Kubo formulation for thermal conductivity was decomposed into self-correlations and cross-correlations of different species and the kinetic, potential, collision and enthalpy terms of the dominant portion of the heat current vector. The presence of liquid layering around the nanoparticle was firmly established through simulations that show the dominant contribution of Ar-Ar self-correlation and the trend displayed by the kinetic-potential cross-correlation within the argon species.

  15. Empirical Formulae for The Calculation of Austenite Supercooled Transformation Temperatures

    Directory of Open Access Journals (Sweden)

    Trzaska J.

    2015-04-01

    Full Text Available The paper presents empirical formulae for the calculation of austenite supercooled transformation temperatures, basing on the chemical composition, austenitising temperature and cooling rate. The multiple regression method was used. Four equations were established allowing to calculate temperature of the start area of ferrite, perlite, bainite and martensite at the given cooling rate. The calculation results obtained do not allow to determine the cooling rate range of ferritic, pearlitic, bainitic and martensite transformations. Classifiers based on logistic regression or neural network were established to solve this problem.

  16. The freezing and supercooling of garlic (Allium sativum L.)

    Energy Technology Data Exchange (ETDEWEB)

    James, Christian; Seignemartin, Violaine; James, Stephen J. [Food Refrigeration and Process Engineering Research Centre (FRPERC), University of Bristol, Churchill Building, Langford, Bristol BS40 5DU (United Kingdom)

    2009-03-15

    This work shows that peeled garlic cloves demonstrate significant supercooling during freezing under standard conditions and can be stored at temperatures well below their freezing point (-2.7 C) without freezing. The nucleation point or 'metastable limit temperature' (the point at which ice crystal nucleation is initiated) of peeled garlic cloves was found to be between -7.7 and -14.6 C. Peeled garlic cloves were stored under static air conditions at temperatures between -6 and -9 C for up to 69 h without freezing, and unpeeled whole garlic bulbs and cloves were stored for 1 week at -6 C without freezing. (author)

  17. Molecular dynamics simulation of cyclodextrin aggregation and extraction of Anthracene from non-aqueous liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xinzhe [Shenzhen Key Laboratory for Coastal Ocean Dynamic and Environment, Division of Ocean Science and Technology, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); School of Environment, Tsinghua University, Beijing 100084 (China); Wu, Guozhong [Shenzhen Key Laboratory for Coastal Ocean Dynamic and Environment, Division of Ocean Science and Technology, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Chen, Daoyi, E-mail: chen.daoyi@sz.tsinghua.edu.cn [Shenzhen Key Laboratory for Coastal Ocean Dynamic and Environment, Division of Ocean Science and Technology, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)

    2016-12-15

    Cyclodextrin (CD) extraction is widely used for the remediation of polycyclic aromatic hydrocarbons (PAH) pollution, but it remains unclear about the influence of CD aggregation on the PAH transport from non-aqueous liquid phase to water. The atomistic adsorption and complexation of PAHs (32 anthracenes) by CD aggregates (48 β-cyclodextrins) were studied by molecular dynamics simulations at hundreds of nanoseconds time scale. Results indicated that high temperature promoted the βCD aggregation in bulk oil, which was not found in bulk water. Nevertheless, the fractions of anthracenes entrapped inside the βCDs cavity in both scenarios were significantly increased when temperature increased from 298 to 328 K. Free energy calculation for the sub-steps of CD extraction demonstrated that the anthracenes could be extracted when the βCDs arrived at the water-oil interface or after the βCDs entered the bulk oil. The former was kinetic-controlled while the latter was thermodynamic-limited process. Results also highlighted the formation of porous structures by CD aggregates in water, which was able to sequestrate PAH clusters with the size obviously larger than the cavity diameter of individual CD. This provided an opportunity for the extraction of recalcitrant PAHs with molecular size larger than anthracenes by cyclodextrins.

  18. Probing spatial heterogeneity in supercooled glycerol and temporal heterogeneity with single-molecule FRET in polyprolines

    NARCIS (Netherlands)

    Xia, Ted

    2010-01-01

    This thesis presents two lines of research. On the one hand, we investigate heterogeneity in supercooled glycerol by means of rheometry, small-angle neutron scattering, and fluorescence imaging. We find from the rheological experiments that supercooled glycerol can behave like weak solids at

  19. Complex bud architecture and cell-specific chemical patterns enable supercooling of Picea abies bud primordial

    Science.gov (United States)

    Bud primordia of Picea abies, despite a frozen shoot, stay ice free down to -50 °C by a mechanism termed supercooling whose biophysical and biochemical requirements are poorly understood. Bud architecture was assessed by 3D-reconstruction, supercooling and freezing patterns by infrared video thermog...

  20. Rapid Analysis of Apolar Low Molecular Weight Constituents in Wood Using High Pressure Liquid Chromatography with Evaporative Light Scattering Detection

    NARCIS (Netherlands)

    Claassen, F.W.; Haar, van de C.; Beek, van T.A.; Dorado, J.; Martinez-Inigo, M.; Sierra-Alvarez, R.

    2000-01-01

    A new high pressure liquid chromatographic method with evaporative light scattering detection was developed for the qualitative and quantitative analysis of apolar, low molecular weight constituents in wood. The wood extractives were obtained by means of a 6 h Soxhlet extraction with acetone. The

  1. Controlling the color of cholesteric liquid-crystalline films by photoirradiation of a chiroptical molecular switch used as dopant

    NARCIS (Netherlands)

    van Delden, RA; Huck, NPM; Feringa, BL; Delden, Richard A. van; Gelder, Marc B. van; Huck, Nina P.M.

    Using thin films of a cholesteric mixture of acrylates 2 and 3 doped with the chiroptical molecular switch (M)-trans-1, photo-control of the reflection color between red and green is possible. This doped liquid-crystal (LC) film can be used for photoinduced writing, color reading, and photoinduced

  2. Comparison of atomic-level and coarse-grained models for liquid hydrocarbons from molecular dynamics configurational entropy estimates

    NARCIS (Netherlands)

    Baron, R; de Vries, AH; Hunenberger, PH; van Gunsteren, WF

    2006-01-01

    Molecular liquids can be modeled at different levels of spatial resolution. In atomic-level (AL) models, all (heavy) atoms can be explicitly simulated. In coarse-grained (CG) models, particles (beads) that represent groups of covalently bound atoms are used as elementary units. Ideally, a CG model

  3. Deuteron-NMR investigation on the dynamics of supercooled, confined water

    Energy Technology Data Exchange (ETDEWEB)

    Sattig, Matthias; Vogel, Michael [TU Darmstadt, Institut fuer Festkoerperphysik (Germany)

    2013-07-01

    The dynamical behaviour of water in the regime of the supercooled liquid is a topic of large interest. In particular, the existence of a fragile-to-strong transition (FST) at T=225K related to the transition between two distinct phases of liquid water is controversially discussed. Due to crystallization the temperature range proposed for the FST is hardly accessible in bulk water. Therefore, we confine heavy water to narrow pores in the mesoporous silicate MCM-41. This suppresses the freezing of a substantial fraction of water, enabling direct investigation of the interesting temperatures. Deuteron-NMR methods are utilised to determine the rotational correlation times τ of water on time scales from ns up to s. The spin-lattice-relaxation time T{sub 1} exhibits a typical minimum at about T = 230 K. Above this minimum the correlation times follow a Vogel-Fulcher-Tammann law. Below the minimum, two relaxation processes could be observed. The low-temperature processes show a different temperature dependence, where the curves τ(T) of all processes intersect at about T = 230 K. A comparison with literature data from neutron scattering and dielectric spectroscopy gives rise to the idea that the observed crossover is due to this intersection of processes rather than to a FST. To test this idea studies on water confined to MCM-41 with different pore sizes and fillings are in progress.

  4. Molecular dynamics studies of the transient nucleation regime in the freezing of (RbCl)108 clusters

    International Nuclear Information System (INIS)

    Huang, Jinfan; Bartell, L.S.Lawrence S.

    2004-01-01

    The freezing of supercooled liquids in the transient period before a steady state of nucleation is attained has been the subject of a number of theoretical treatments. To our knowledge, no published experimental studies or computer simulations have been carried out in sufficient detail to test definitively the behavior predicted by the various theories. The present molecular dynamics (MD) simulation of 375 nucleation events in small, liquid RbCl clusters, however, yields a reasonably accurate account of the transient region. Despite published criticisms of a 1969 treatment by Kashchiev, it turns out that the behavior observed in the present study agrees with that predicted by Kashchiev. The study also obtains a much more accurate nucleation rate and time lag than reported for MD studies of RbCl previously published in this journal. In addition, it provides estimates of the solid-liquid interfacial free energy and the Granasy thickness of the diffuse solid-liquid interface

  5. Xylem development in prunus flower buds and the relationship to deep supercooling.

    Science.gov (United States)

    Ashworth, E N

    1984-04-01

    Xylem development in eight Prunus species was examined and the relationship to deep supercooling assessed. Dormant buds of six species, P. armeniaca, P. avium, P. cerasus, P. persica, P. salicina, and P. sargentii deep supercooled. Xylem vessel elements were not observed within the dormant floral primordia of these species. Instead, discrete bundles containing procambial cells were observed. Vascular differentiation resumed and xylem continuity was established during the time that the capacity to deep supercool was lost. In P. serotina and P. virginiana, two species which do not supercool, xylem vessels ran the length of the inflorescence and presumably provided a conduit for the spread of ice into the bud. The results support the hypothesis that the lack of xylem continuity is an important feature of buds which deep supercool.

  6. A review of the structure and dynamics of nanoconfined water and ionic liquids via molecular dynamics simulation.

    Science.gov (United States)

    Foroutan, Masumeh; Fatemi, S Mahmood; Esmaeilian, Farshad

    2017-02-01

    During the past decade, the research on fluids in nanoconfined geometries has received considerable attention as a consequence of their wide applications in different fields. Several nanoconfined systems such as water and ionic liquids, together with an equally impressive array of nanoconfining media such as carbon nanotube, graphene and graphene oxide have received increasingly growing interest in the past years. Water is the first system that has been reviewed in this article, due to its important role in transport phenomena in environmental sciences. Water is often considered as a highly nanoconfined system, due to its reduction to a few layers of water molecules between the extended surface of large macromolecules. The second system discussed here is ionic liquids, which have been widely studied in the modern green chemistry movement. Considering the great importance of ionic liquids in industry, and also their oil/water counterpart, nanoconfined ionic liquid system has become an important area of research with many fascinating applications. Furthermore, the method of molecular dynamics simulation is one of the major tools in the theoretical study of water and ionic liquids in nanoconfinement, which increasingly has been joined with experimental procedures. In this way, the choice of water and ionic liquids in nanoconfinement is justified by applying molecular dynamics simulation approaches in this review article.

  7. On the Fluctuations that Order and Frustrate Liquid Water

    Science.gov (United States)

    Limmer, David Tyler

    At ambient conditions, water sits close to phase coexistence with its crystal. More so than in many other materials, this fact is manifested in the fluctuations that maintain a large degree of local order in the liquid. These fluctuations and how they result in long-ranged order, or its absence, are emergent features of many interacting molecules. Their study therefore requires using the tools of statistical mechanics for their their systematic understanding. In this dissertation we develop such an understanding. In particular, we focus on collective behavior that emerges in liquid and solid water. At room temperatures, the thermophysical properties of water are quantified and rationalized with simple molecular models. A key feature of these models is the correct characterization of the competition between entropic forces of packing and the energetic preference for tetrahedral order. At cold temperatures, the properties of ice surfaces are studied with statistical field theory. The theory we develop for the long wavelength features of ice interfaces allows us to explain the existence of a premelting layer on the surface of ice and the stability of ice in confinement. In between these extremes, the dynamics of supercooled water are considered. A detailed theory for the early stages of coarsening is developed and used to explain the peculiar observation of a transient second liquid state of water. When coarsening dynamics are arrested, the result is the formation of a glassy states of water. We show that out-of-equilibrium the phase diagram for supercooled water exhibits a rich amount of structure, including a triple point between two glass phases of water and the liquid. At the end, we explore possible technological implications for the interplay between ordering and frustration in studies of water at metal interfaces.

  8. Resolving dispersion and induction components for polarisable molecular simulations of ionic liquids

    Science.gov (United States)

    Pádua, Agílio A. H.

    2017-05-01

    One important development in interaction potential models, or atomistic force fields, for molecular simulation is the inclusion of explicit polarisation, which represents the induction effects of charged or polar molecules on polarisable electron clouds. Polarisation can be included through fluctuating charges, induced multipoles, or Drude dipoles. This work uses Drude dipoles and is focused on room-temperature ionic liquids, for which fixed-charge models predict too slow dynamics. The aim of this study is to devise a strategy to adapt existing non-polarisable force fields upon addition of polarisation, because induction was already contained to an extent, implicitly, due to parametrisation against empirical data. Therefore, a fraction of the van der Waals interaction energy should be subtracted so that the Lennard-Jones terms only account for dispersion and the Drude dipoles for induction. Symmetry-adapted perturbation theory is used to resolve the dispersion and induction terms in dimers and to calculate scaling factors to reduce the Lennard-Jones terms from the non-polarisable model. Simply adding Drude dipoles to an existing fixed-charge model already improves the prediction of transport properties, increasing diffusion coefficients, and lowering the viscosity. Scaling down the Lennard-Jones terms leads to still faster dynamics and densities that match experiment extremely well. The concept developed here improves the overall prediction of density and transport properties and can be adapted to other models and systems. In terms of microscopic structure of the ionic liquids, the inclusion of polarisation and the down-scaling of Lennard-Jones terms affect only slightly the ordering of the first shell of counterions, leading to small decreases in coordination numbers. Remarkably, the effect of polarisation is major beyond first neighbours, significantly weakening spatial correlations, a structural effect that is certainly related to the faster dynamics of

  9. Extended Smoluchowski models for interpreting relaxation phenomena in liquids

    International Nuclear Information System (INIS)

    Polimeno, A.; Frezzato, D.; Saielli, G.; Moro, G.J.; Nordio, P.L.

    1998-01-01

    Interpretation of the dynamical behaviour of single molecules or collective modes in liquids has been increasingly centered, in the last decade, on complex liquid systems, including ionic solutions, polymeric liquids, supercooled fluids and liquid crystals. This has been made necessary by the need of interpreting dynamical data obtained by advanced experiments, like optical Kerr effect, time dependent fluorescence shift experiments, two-dimensional Fourier-transform and high field electron spin resonance and scattering experiments like quasi-elastic neutron scattering. This communication is centered on the definition, treatment and application of several extended stochastic models, which have proved to be very effective tools for interpreting and rationalizing complex relaxation phenomena in liquids structures. First, applications of standard Fokker-Planck equations for the orientational relaxation of molecules in isotropic and ordered liquid phase are reviewed. In particular attention will be focused on the interpretation of neutron scattering in nematics. Next, an extended stochastic model is used to interpret time-domain resolved fluorescence emission experiments. A two-body stochastic model allows the theoretical interpretation of dynamical Stokes shift effects in fluorescence emission spectra, performed on probes in isotropic and ordered polar phases. Finally, for the case of isotropic fluids made of small rigid molecules, a very detailed model is considered, which includes as basic ingredients a Fokker-Planck description of the molecular vibrational motion and the slow diffusive motion of a persistent cage structure together with the decay processes related to the changing structure of the cage. (author)

  10. Dynamical heterogeneities of rotational motion in room temperature ionic liquids evidenced by molecular dynamics simulations

    Science.gov (United States)

    Usui, Kota; Hunger, Johannes; Bonn, Mischa; Sulpizi, Marialore

    2018-05-01

    Room temperature ionic liquids (RTILs) have been shown to exhibit spatial heterogeneity or structural heterogeneity in the sense that they form hydrophobic and ionic domains. Yet studies of the relationship between this structural heterogeneity and the ˜picosecond motion of the molecular constituents remain limited. In order to obtain insight into the time scales relevant to this structural heterogeneity, we perform molecular dynamics simulations of a series of RTILs. To investigate the relationship between the structures, i.e., the presence of hydrophobic and ionic domains, and the dynamics, we gradually increase the size of the hydrophobic part of the cation from ethylammonium nitrate (EAN), via propylammonium nitrate (PAN), to butylammonium nitrate (BAN). The two ends of the organic cation, namely, the charged Nhead-H group and the hydrophobic Ctail-H group, exhibit rotational dynamics on different time scales, evidencing dynamical heterogeneity. The dynamics of the Nhead-H group is slower because of the strong coulombic interaction with the nitrate counter-ionic anions, while the dynamics of the Ctail-H group is faster because of the weaker van der Waals interaction with the surrounding atoms. In particular, the rotation of the Nhead-H group slows down with increasing cationic chain length, while the rotation of the Ctail-H group shows little dependence on the cationic chain length, manifesting that the dynamical heterogeneity is enhanced with a longer cationic chain. The slowdown of the Nhead-H group with increasing cationic chain length is associated with a lower number of nitrate anions near the Nhead-H group, which presumably results in the increase of the energy barrier for the rotation. The sensitivity of the Nhead-H rotation to the number of surrounding nitrate anions, in conjunction with the varying number of nitrate anions, gives rise to a broad distribution of Nhead-H reorientation times. Our results suggest that the asymmetry of the cations and the

  11. Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

    Science.gov (United States)

    Tentscher, Peter R; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J; Arey, J Samuel

    2015-01-08

    To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

  12. Thermodynamic properties by equation of state and from Ab initio molecular dynamics of liquid potassium under pressure

    Science.gov (United States)

    Li, Huaming; Tian, Yanting; Sun, Yongli; Li, Mo; Nonequilibrium materials; physics Team; Computational materials science Team

    In this work, we apply a general equation of state of liquid and Ab initio molecular-dynamics method to study thermodynamic properties in liquid potassium under high pressure. Isothermal bulk modulus and molar volume of molten sodium are calculated within good precision as compared with the experimental data. The calculated internal energy data and the calculated values of isobaric heat capacity of molten potassium show the minimum along the isothermal lines as the previous result obtained in liquid sodium. The expressions for acoustical parameter and nonlinearity parameter are obtained based on thermodynamic relations from the equation of state. Both parameters for liquid potassium are calculated under high pressure along the isothermal lines by using the available thermodynamic data and numeric derivations. Furthermore, Ab initio molecular-dynamics simulations are used to calculate some thermodynamic properties of liquid potassium along the isothermal lines. Scientific Research Starting Foundation from Taiyuan university of Technology, Shanxi Provincial government (``100-talents program''), China Scholarship Council and National Natural Science Foundation of China (NSFC) under Grant No. 51602213.

  13. Neutron Scattering of Residual Hydrogen in 1,4-Dioxane-D8 Liquid. Understanding Measurements with Molecular Dynamics Simulations

    Energy Technology Data Exchange (ETDEWEB)

    de Almeida, Valmor F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Liu, Hongjun [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Herwig, Kenneth W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kidder, Michelle [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-01-25

    That incoherent scattering from protiated molecular liquids adds a constant background to the measured scattering intensity is well known, but less appreciated is the fact that coherent scattering is also induced by the presence of hydrogen in a deuterated liquid. In fact, the scattering intensity can be very sensitive, in the small-q region, with respect to the amounts and distribution of residual H in the system. We used 1,4-dioxane liquid to demonstrate that the partial structure factors of the HD and DD atom pairs contribute significantly to inter-molecular scattering and that uncertainty in the extent of deuteration account for discrepancies between simulations and measurements. Both contributions to uncertainty have similar magnitudes: scattering interference of the hydrogen-deuterium pair, and complementary interference from the deuterium-deuterium pair by virtue of chemical inhomogeneity. This situation arises in practice since deuteration of liquids is often 99% or less. A combined experimental and extensive computational study of static thermal neutron scattering of 1,4-dioxane demonstrates the foregoing. We show, through simulations, that the reason for the differences is the content of protiated dioxane (vendors quote 1%). We estimate that up to 5% (at 298K and at 343K) protiated mole fraction may be involved in generating the scattering differences. Finally, we find that the particular distribution of hydrogen in the protiated molecules affects the results significantly; here we considered molecules to be either fully protiated or fully deuterated. This scenario best reconciles the computational and experimental results, and leads us to speculate that the deuteration synthesis process tends to leave a molecule either fully deuterated or fully protiated. Although we have used 1,4-dioxane as a model liquid, the effects described in this study extend to similar liquids and similar systematic experimental/computational studies can be performed to either

  14. Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study

    Science.gov (United States)

    Weyman, Alexander; Bier, Markus; Holm, Christian; Smiatek, Jens

    2018-05-01

    We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids. The ion transport numbers are unaffected by the occurrence of these domains, and the corresponding values highlight the potential role of PILs as single-ion conductors in electrochemical devices. In contrast to bulk behavior, a pronounced formation of ion conductivity channels in confined systems is initiated in close vicinity to the boundaries. We observe higher ion conductivities in these channels for increasing PIL side chain lengths in comparison with bulk values and provide an explanation for this effect. The appearance of these domains points to an improved application of PILs in modern polymer electrolyte batteries.

  15. Behavior of protruding lateral plane graphene sheets in liquid dodecane: molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Shenghui; Sun, Shuangqing, E-mail: sunshuangqing@upc.edu.cn; Li, Chunling [China University of Petroleum (East China), College of Science (China); Pittman, Charles U. [Mississippi State University, Department of Chemistry (United States); Lacy, Thomas E. [Mississippi State University, Department of Aerospace Engineering (United States); Hu, Songqing, E-mail: songqinghu@upc.edu.cn [China University of Petroleum (East China), College of Science (China); Gwaltney, Steven R. [Mississippi State University, Department of Chemistry (United States)

    2016-11-15

    Molecular dynamics simulations are used to investigate the behavior of two parallel graphene sheets fixed on one edge (lateral plane) in liquid dodecane. The interactions of these sheets and dodecane molecules are studied with different starting inter-sheet distances. The structure of the dodecane solvent is also analyzed. The results show that when the distance between the two graphene sheets is short (less than 6.8 Å), the sheets will expel the dodecane molecules between them and stack together. However, when the distance between two sheets is large (greater than 10.2 Å), the two sheets do not come together, and the dodecane molecules will form ordered layers in the interlayer spacing. The equilibrium distance between the graphene sheets can only take on specific discrete values (3.4, 7.8, and 12.1 Å), because only an integer number of dodecane layers forms between the two sheets. Once the graphene sheets are in contact, they remain in contact; the sheets do not separate to allow dodecane into the interlayer spacing.

  16. Molecular dynamics simulation of metallic impurity diffusion in liquid lead-bismuth eutectic (LBE)

    Science.gov (United States)

    Gao, Yun; Takahashi, Minoru; Cavallotti, Carlo; Raos, Guido

    2018-04-01

    Corrosion of stainless steels by lead-bismuth eutectic (LBE) is an important problem which depends, amongst other things, on the diffusion of the steel components inside this liquid alloy. Here we present the results of classical molecular dynamics simulations of the diffusion of Fe and Ni within LBE. The simulations complement experimental studies of impurity diffusion by our group and provide an atomic-level understanding of the relevant diffusion phenomena. They are based on the embedded atom method (EAM) to represent many-body interactions among atoms. The EAM potentials employed in our simulations have been validated against ab initio density functional calculations. We show that the experimental and simulation results for the temperature-dependent viscosity of LBE and the impurity diffusion coefficients can be reconciled by assuming that the Ni and Fe diffuse mainly as nanoscopic clusters below 1300 K. The average Fe and Ni cluster sizes decrease with increasing the temperature and there is essentially single-atom diffusion at higher temperatures.

  17. Er Effect of Low Molecular Liquid Crystal on One-Sided Patterned Electrodes

    Science.gov (United States)

    Kikuchi, Takehito; Inoue, Akio; Furusho, Junji; Kawamuki, Ryohei

    Several kinds of ER fluids (ERF) have been developed and have been applied to some mechatronics devices and processing technologies. In many conventional applications of ERFs, these devices consist of bilateral electrodes to apply electric field in ERF. However, the electric field of several kV/mm may be necessary to generate an ER effect sufficiently for practical purposes. The gap between a pair of electrodes should be, therefore, maintained narrowly and exactly for fears of short-circuit. At the same time, this electrode system also requires an interconnection on driving parts. To improve these disadvantages, we proposed "one-sided patterned electrode" (OSPE) systems in previous works. In this report, we confirmed the flow characteristics of low molecular liquid crystal (LMLC) on OSPE. Next, we also confirmed the different characteristics depending on the pattern type. Depending on results of electro-static analysis, we conclude that such a difference may results from the directors of LC molecules derived by electric field.

  18. Effects of molecular elongation on liquid crystalline phase behaviour: isotropic-nematic transition

    Science.gov (United States)

    Singh, Ram Chandra; Ram, Jokhan

    2003-08-01

    We present the density-functional approach to study the isotropic-nematic transitions and calculate the values of freezing parameters of the Gay-Berne liquid crystal model, concentrating on the effects of varying the molecular elongation, x0. For this, we have solved the Percus-Yevick integral equation theory to calculate the pair-correlation functions of a fluid the molecules of which interact via a Gay-Berne pair potential. These results have been used in the density-functional theory as an input to locate the isotropic-nematic transition and calculate freezing parameters for a range of length-to-width parameters 3.0⩽ x0⩽4.0 at reduced temperatures 0.95 and 1.25. We observed that as x0 is increased, the isotropic-nematic transition is seen to move to lower density at a given temperature. We find that the density-functional theory is good to study the freezing transitions in such fluids. We have also compared our results with computer simulation results wherever they are available.

  19. Molecular dynamics simulations of polyethers and a quaternary ammonium ionic liquid as CO2 absorbers

    Science.gov (United States)

    Cardoso, Piercarlo Fortunato; Fernandez, Juan S. L. C.; Lepre, Luiz Fernando; Ando, Rômulo Augusto; Costa Gomes, Margarida F.; Siqueira, Leonardo J. A.

    2018-04-01

    The properties of mixtures of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], with poly(ethyleneglycol) dimethyl ether, PEO, were described as a function of PEO chain size by molecular dynamics simulations. Both PEO chain size and mixture composition revealed to play a significant role in determining the structure and the dynamics of the fluids. The remarkably higher viscosity observed for mixtures composed by 0.25 mole fraction of PEO was attributed to the increase in the gauche population of OCCO dihedral of the polyether of longer chains. The negative solvation enthalpy (ΔsolH < 0) and entropy (ΔsolS < 0) revealed a favorable CO2 absorption by the neat and mixture systems. The CO2 absorption was higher in neat PEO, particularly considering longer chains. The gas solubility in the mixtures presented intermediate values in comparison to the neat PEO and neat ionic liquid. The CO2 solutions had their structures discussed in the light of the calculated radial and spatial distribution functions.

  20. Molecular dynamics simulations of Gay-Berne nematic liquid crystal: Elastic properties from direct correlation functions

    International Nuclear Information System (INIS)

    Stelzer, J.; Trebin, H.R.; Longa, L.

    1994-08-01

    We report NVT and NPT molecular dynamics simulations of a Gay-Berne nematic liquid crystal using generalization of recently proposed algorithm by Toxvaerd [Phys. Rev. E47, 343, 1993]. On the basis of these simulations the Oseen-Zoher-Frank elastic constants K 11 , K 22 and K 33 as well as the surface constants K 13 and K 24 have been calculated within the framework of the direct correlation function approach of Lipkin et al. [J. Chem. Phys. 82, 472 (1985)]. The angular coefficients of the direct pair correlation function, which enter the final formulas, have been determined from the computer simulation data for the pair correlation function of the nematic by combining the Ornstein-Zernike relation and the Wienier-Hopf factorization scheme. The unoriented nematic approximation has been assumed when constructing the reference, isotropic state of Lipkin et al. By an extensive study of the model over a wide range of temperatures, densities and pressures a very detailed information has been provided about elastic behaviour of the Gay-Berne nematic. Interestingly, it is found that the results for the surface elastic constants are qualitatively different than those obtained with the help of analytical approximations for the isotropic, direct pair correlation function. For example, the values of the surface elastic constants are negative and an order of magnitude smaller than the bulk elasticity. (author). 30 refs, 9 figs

  1. Molecular dynamic simulation of the atomic structure of aluminum solid–liquid interfaces

    International Nuclear Information System (INIS)

    Men, H; Fan, Z

    2014-01-01

    In this paper, molecular dynamic (MD) simulation was used to investigate the equilibrium atomic arrangement at aluminum solid–liquid (S/L) interfaces with {111}, {110} and {100} orientations. The simulation results reveal that the aluminum S/L interfaces are diffuse for all the orientations, and extend up to 7 atomic layers. Within the diffuse interfaces there exists substantial atomic ordering, which is manifested by atomic layering perpendicular to the interface and in-plane atomic ordering parallel to the interface. Atomic layering can be quantified by the atomic density profile (ρ(z)) while the in-plane atomic ordering can be described by the in-plane ordering parameter (S(z)). The detailed MD simulation suggests that atomic layering at the interface always occurs within 7 atomic layers independent of the interface orientation while the in-plane ordering is highly dependent on the interface orientations, with the {111} interface being less diffuse than the {100} and {110} interfaces. This study demonstrates clearly that the physical origin of the diffuse interface is atomic layering and in-plane atomic ordering at the S/L interfaces. It is suggested that the difference in atomic layering and in-plane ordering at the S/L interface with different orientations is responsible for the observed growth anisotropy. (papers)

  2. Thermophysical properties of energetic ionic liquids/nitric acid mixtures: insights from molecular dynamics simulations.

    Science.gov (United States)

    Hooper, Justin B; Smith, Grant D; Bedrov, Dmitry

    2013-09-14

    Molecular dynamics (MD) simulations of mixtures of the room temperature ionic liquids (ILs) 1-butyl-4-methyl imidazolium [BMIM]/dicyanoamide [DCA] and [BMIM][NO3(-)] with HNO3 have been performed utilizing the polarizable, quantum chemistry based APPLE&P(®) potential. Experimentally it has been observed that [BMIM][DCA] exhibits hypergolic behavior when mixed with HNO3 while [BMIM][NO3(-)] does not. The structural, thermodynamic, and transport properties of the IL/HNO3 mixtures have been determined from equilibrium MD simulations over the entire composition range (pure IL to pure HNO3) based on bulk simulations. Additional (non-equilibrium) simulations of the composition profile for IL/HNO3 interfaces as a function of time have been utilized to estimate the composition dependent mutual diffusion coefficients for the mixtures. The latter have been employed in continuum-level simulations in order to examine the nature (composition and width) of the IL/HNO3 interfaces on the millisecond time scale.

  3. Molecular dynamics calculation of thermophysical properties for a highly reactive liquid.

    Science.gov (United States)

    Wang, H P; Luo, B C; Wei, B

    2008-10-01

    In order to further understand the physical characteristics of liquid silicon, the thermophysical properties are required over a broad temperature range. However, its high reactivity brings about great difficulties in the experimental measurement. Here we report the thermophysical properties by molecular dynamics calculation, including density, specific heat, diffusion coefficient, and surface tension. The calculation is performed with a system consisting of 64,000 atoms, and employing the Stillinger-Weber (SW) potential model and the modified embedded atom method (MEAM) potential model. The results show that the density increases as a quadratic function of undercooling, and the value calculated by SW potential model is only 2-4 % smaller than the reported experimental data. The specific heat is obtained to be 30.95 J mol;{-1}K;{-1} by SW potential model and 32.50 J mol;{-1}K;{-1} by MEAM potential model, both of which are constants in the corresponding ranges of temperature. The self-diffusion coefficient is exponentially dependent on the temperature and consistent with the Arrhenius equation. The surface tension increases linearly with the rise of undercooling and agrees well with the reported experimental results. This work provides reasonable data in much wider temperature range, especially for the undercooled metastable state.

  4. A metastable liquid melted from a crystalline solid under decompression

    Science.gov (United States)

    Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

    2017-01-01

    A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid-solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure-temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.

  5. Seasonal change in the capacity for supercooling by neonatal painted turtles.

    Science.gov (United States)

    Packard, G C; Packard, M J; McDaniel, L L

    2001-05-01

    Hatchlings of the North American painted turtle (Chrysemys picta) typically spend their first winter of life inside the shallow, subterranean nest where they completed incubation the preceding summer. This facet of their natural history commonly causes neonates in northerly populations to be exposed in mid-winter to ice and cold, which many animals survive by remaining unfrozen and supercooled. We measured the limit of supercooling in samples of turtles taken shortly after hatching and in other samples after 2 months of acclimation (or acclimatization) to a reduced temperature in the laboratory or field. Animals initially had only a limited capacity for supercooling, but they acquired an ability to undergo deeper supercooling during the course of acclimation. The gut of most turtles was packed with particles of soil and eggshell shortly after hatching, but not after acclimation. Thus, the relatively high limit of supercooling for turtles in the days immediately after hatching may have resulted from the ingestion of soil (and associated nucleating agents) by the animals as they were freeing themselves from their eggshell, whereas the relatively low limit of supercooling attained by acclimated turtles may have resulted from their purging their gut of its contents. Parallels may, therefore, exist between the natural-history strategy expressed by hatchling painted turtles and that expressed by numerous terrestrial arthropods that withstand the cold of winter by sustaining a state of supercooling.

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

    Science.gov (United States)

    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.

  7. Quantum molecular dynamics simulations of the thermophysical properties of shocked liquid ammonia for pressures up to 1.3 TPa.

    Science.gov (United States)

    Li, Dafang; Zhang, Ping; Yan, Jun

    2013-10-07

    We investigate via quantum molecular-dynamics simulations the thermophysical properties of shocked liquid ammonia up to the pressure 1.3 TPa and temperature 120,000 K. The principal Hugoniot is predicted from the wide-range equation of state, which agrees well with the available experimental measurements up to 64 GPa. Our systematic study of the structural properties demonstrates that the liquid ammonia undergoes a gradual phase transition along the Hugoniot. At about 4800 K, the system transforms into a metallic, complex mixture state consisting of NH3, N2, H2, N, and H. Furthermore, we discuss the implications for the interiors of Uranus and Neptune.

  8. Molecular dynamics simulations of hydrophobous ions at the liquid-liquid interfaces: case of dicarbollide anions as synergy agents and of ionic liquids as extracting medium; Simulations par dynamique moleculaire d'ions hydrophobes aux interfaces liquide - liquide: le cas des anions dicarbollides comme agents de synergie et celui des liquides ioniques comme milieu extractant

    Energy Technology Data Exchange (ETDEWEB)

    Chevrot, G

    2008-01-15

    Based on molecular dynamics simulations, we first describe the distribution of dicarbollide salts (CCD{sup -}, Mn{sup +}) in concentrated monophasic solutions (water, chloroform, octanol, nitrobenzene) and in the corresponding biphasic 'oil' - water solutions. We point to the importance of surface activity of the CCD{sup -}s and of their self-aggregation in water, with marked counterions effects, and we explain the synergistic effect of CCD{sup -}s in the Eu{sup 3+} extraction by BTP ligands. In the second part of the thesis we report exploratory simulations on the extraction of Sr{sup 2+} by 18-crown-6 to an hydrophobic ionic liquid ([BMI][PF6]), focusing on the liquid - liquid interface. Analogies and differences with a classical aqueous interface are outlined. (author)

  9. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

    Science.gov (United States)

    Kanno, H.; Kajiwara, K.; Miyata, K.

    2010-05-01

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  10. Superheating and supercooling of Ge nanocrystals embedded in SiO2

    International Nuclear Information System (INIS)

    Xu, Q; Sharp, I D; Yuan, C W; Yi, D O; Liao, C Y; Glaeser, A M; Minor, A M; Beeman, J W; Ridgway, M C; Kluth, P; Iii, J W Ager; Chrzan, D C; Haller, E E

    2007-01-01

    Free-standing nanocrystals exhibit a size-dependant thermodynamic melting point reduction relative to the bulk melting point that is governed by the surface free energy. The presence of an encapsulating matrix, however, alters the interface free energy of nanocrystals and their thermodynamic melting point can either increase or decrease relative to bulk. Furthermore, kinetic contributions can significantly alter the melting behaviours of embedded nanoscale materials. To study the effect of an encapsulating matrix on the melting behaviour of nanocrystals, we performed in situ electron diffraction measurements on Ge nanocrystals embedded in a silicon dioxide matrix. Ge nanocrystals were formed by multi-energy ion implantation into a 500 nm thick silica thin film on a silicon substrate followed by thermal annealing at 900 deg. C for 1 h. We present results demonstrating that Ge nanocrystals embedded in SiO 2 exhibit a 470 K melting/solidification hysteresis that is approximately symmetric about the bulk melting point. This unique behaviour, which is thought to be impossible for bulk materials, is well described using a classical thermodynamic model that predicts both kinetic supercooling and kinetic superheating. The presence of the silica matrix suppresses surface pre-melting of nanocrystals. Therefore, heterogeneous nucleation of both the liquid phase and the solid phase are required during the heating and cooling cycle. The magnitude of melting hysteresis is governed primarily by the value of the liquid Ge/solid Ge interface free energy, whereas the relative values of the solid Ge/matrix and liquid Ge/matrix interface free energies govern the position of the hysteresis loop in absolute temperature

  11. Experimental investigations on cylindrical latent heat storage units with sodium acetate trihydrate composites utilizing supercooling

    DEFF Research Database (Denmark)

    Dannemand, Mark; Johansen, Jakob Berg; Kong, Weiqiang

    2016-01-01

    Latent heat storage units utilizing stable supercooling of sodium acetate trihydrate (SAT) composites were tested in a laboratory. The stainless steel units were 1.5 m high cylinders with internal heat exchangers of tubes with fins. One unit was tested with 116 kg SAT with 6% extra water. Another...... in the thickened phase change material after melting. The heat content in the fully charged state and the heat released after solidification of the supercooled SAT mixtures at ambient temperature was higher for the unit with the thickened SAT mixture. The heat discharged after solidification of the supercooled SAT...

  12. Laboratory test of a prototype heat storage module based on stable supercooling of sodium acetate trihydrate

    DEFF Research Database (Denmark)

    Dannemand, Mark; Kong, Weiqiang; Fan, Jianhua

    2015-01-01

    Laboratory test of a long term heat storage module utilizing the principle of stable supercooling of 199.5 kg of sodium acetate water mixture has been carried out. Avoiding phase separation of the incongruently melting salt hydrate by using the extra water principle increased the heat storage...... capacity. An external expansion vessel minimized the pressure built up in the module while heating and reduced the risk of instable supercooling. The module was stable supercooled at indoor ambient temperature for up to two months after which it was discharged. The energy discharged after activating...

  13. Long term thermal energy storage with stable supercooled sodium acetate trihydrate

    DEFF Research Database (Denmark)

    Dannemand, Mark; Schultz, Jørgen M.; Johansen, Jakob Berg

    2015-01-01

    Utilizing stable supercooling of sodium acetate trihydrate makes it possible to store thermal energy partly loss free. This principle makes seasonal heat storage in compact systems possible. To keep high and stable energy content and cycling stability phase separation of the storage material must...... it expands and will cause a pressure built up in a closed chamber which might compromise stability of the supercooling. This can be avoided by having an air volume above the phase change material connected to an external pressure less expansion tank. Supercooled sodium acetate trihydrate at 20 °C stores up...

  14. Theory of terahertz electric oscillations by supercooled superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Mishonov, Todor M; Mishonov, Mihail T [Department of Theoretical Physics, Faculty of Physics, University of Sofia St Kliment Ohridski, 5 J Bourchier Boulevard, 1164 Sofia (Bulgaria); Laboratorium voor Vaste-Stoffysica en Magnetisme, Katholieke Universiteit Leuven, Celestijnenlaan 200 D B-3001 Leuven (Belgium)

    2005-11-15

    We predict that below T{sub c} a regime of negative differential conductivity (NDC) can be reached. The superconductor should be supercooled to Tsupercooled superconductors to be used as an active medium for generation of electric oscillations. Such generators can be used in the superconducting electronics as a new type THz source of radiation. Oscillations can be modulated by the change of the bias voltage, electrostatic doping by a gate electrode when the superconductor is the channel of a field effect transistor, or by light. When small amplitude oscillations are stabilized near the critical temperature T{sub c} the generator can be used as a bolometer. NDC, which is essential for the applications, is predicted on the basis of analysis of known results for fluctuation conductivity, obtained in previous papers by solving the Boltzmann kinetic equation for the Cooper pairs metastable in the normal phase. The Boltzmann equation for fluctuation Cooper pairs is a result of state-of-the-art application of the microscopic theory of superconductivity. Our theoretical conclusions are based on some approximations like time dependent Ginzburg-Landau theory initially derived for gapless superconductors, but nevertheless can reliably predict the appearance of NDC. NDC is the main ingredient of the proposed technical applications. The maximal frequency at which superconductors can operate as generators is determined by the critical temperature {Dirac_h}/2{pi}{omega}{sub max} {approx} k{sub B}T{sub c}. For high-T{sub c} superconductors this maximal frequency falls well inside the terahertz range. Technical conditions to avoid nucleation of the superconducting phase are briefly discussed. We suggest that nanostructured high-T{sub c} superconductors patterned in a single chip can

  15. Multi-scale coarse-graining of non-conservative interactions in molecular liquids

    International Nuclear Information System (INIS)

    Izvekov, Sergei; Rice, Betsy M.

    2014-01-01

    A new bottom-up procedure for constructing non-conservative (dissipative and stochastic) interactions for dissipative particle dynamics (DPD) models is described and applied to perform hierarchical coarse-graining of a polar molecular liquid (nitromethane). The distant-dependent radial and shear frictions in functional-free form are derived consistently with a chosen form for conservative interactions by matching two-body force-velocity and three-body velocity-velocity correlations along the microscopic trajectories of the centroids of Voronoi cells (clusters), which represent the dissipative particles within the DPD description. The Voronoi tessellation is achieved by application of the K-means clustering algorithm at regular time intervals. Consistently with a notion of many-body DPD, the conservative interactions are determined through the multi-scale coarse-graining (MS-CG) method, which naturally implements a pairwise decomposition of the microscopic free energy. A hierarchy of MS-CG/DPD models starting with one molecule per Voronoi cell and up to 64 molecules per cell is derived. The radial contribution to the friction appears to be dominant for all models. As the Voronoi cell sizes increase, the dissipative forces rapidly become confined to the first coordination shell. For Voronoi cells of two and more molecules the time dependence of the velocity autocorrelation function becomes monotonic and well reproduced by the respective MS-CG/DPD models. A comparative analysis of force and velocity correlations in the atomistic and CG ensembles indicates Markovian behavior with as low as two molecules per dissipative particle. The models with one and two molecules per Voronoi cell yield transport properties (diffusion and shear viscosity) that are in good agreement with the atomistic data. The coarser models produce slower dynamics that can be appreciably attributed to unaccounted dissipation introduced by regular Voronoi re-partitioning as well as by larger

  16. On the equilibrium contact angle of sessile liquid drops from molecular dynamics simulations.

    Science.gov (United States)

    Ravipati, Srikanth; Aymard, Benjamin; Kalliadasis, Serafim; Galindo, Amparo

    2018-04-28

    We present a new methodology to estimate the contact angles of sessile drops from molecular simulations by using the Gaussian convolution method of Willard and Chandler [J. Phys. Chem. B 114, 1954-1958 (2010)] to calculate the coarse-grained density from atomic coordinates. The iso-density contour with average coarse-grained density value equal to half of the bulk liquid density is identified as the average liquid-vapor (LV) interface. Angles between the unit normal vectors to the average LV interface and unit normal vector to the solid surface, as a function of the distance normal to the solid surface, are calculated. The cosines of these angles are extrapolated to the three-phase contact line to estimate the sessile drop contact angle. The proposed methodology, which is relatively easy to implement, is systematically applied to three systems: (i) a Lennard-Jones (LJ) drop on a featureless LJ 9-3 surface; (ii) an SPC/E water drop on a featureless LJ 9-3 surface; and (iii) an SPC/E water drop on a graphite surface. The sessile drop contact angles estimated with our methodology for the first two systems are shown to be in good agreement with the angles predicted from Young's equation. The interfacial tensions required for this equation are computed by employing the test-area perturbation method for the corresponding planar interfaces. Our findings suggest that the widely adopted spherical-cap approximation should be used with caution, as it could take a long time for a sessile drop to relax to a spherical shape, of the order of 100 ns, especially for water molecules initiated in a lattice configuration on a solid surface. But even though a water drop can take a long time to reach the spherical shape, we find that the contact angle is well established much faster and the drop evolves toward the spherical shape following a constant-contact-angle relaxation dynamics. Making use of this observation, our methodology allows a good estimation of the sessile drop contact

  17. Multi-scale coarse-graining of non-conservative interactions in molecular liquids

    Energy Technology Data Exchange (ETDEWEB)

    Izvekov, Sergei, E-mail: sergiy.izvyekov.civ@mail.mil; Rice, Betsy M. [U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States)

    2014-03-14

    A new bottom-up procedure for constructing non-conservative (dissipative and stochastic) interactions for dissipative particle dynamics (DPD) models is described and applied to perform hierarchical coarse-graining of a polar molecular liquid (nitromethane). The distant-dependent radial and shear frictions in functional-free form are derived consistently with a chosen form for conservative interactions by matching two-body force-velocity and three-body velocity-velocity correlations along the microscopic trajectories of the centroids of Voronoi cells (clusters), which represent the dissipative particles within the DPD description. The Voronoi tessellation is achieved by application of the K-means clustering algorithm at regular time intervals. Consistently with a notion of many-body DPD, the conservative interactions are determined through the multi-scale coarse-graining (MS-CG) method, which naturally implements a pairwise decomposition of the microscopic free energy. A hierarchy of MS-CG/DPD models starting with one molecule per Voronoi cell and up to 64 molecules per cell is derived. The radial contribution to the friction appears to be dominant for all models. As the Voronoi cell sizes increase, the dissipative forces rapidly become confined to the first coordination shell. For Voronoi cells of two and more molecules the time dependence of the velocity autocorrelation function becomes monotonic and well reproduced by the respective MS-CG/DPD models. A comparative analysis of force and velocity correlations in the atomistic and CG ensembles indicates Markovian behavior with as low as two molecules per dissipative particle. The models with one and two molecules per Voronoi cell yield transport properties (diffusion and shear viscosity) that are in good agreement with the atomistic data. The coarser models produce slower dynamics that can be appreciably attributed to unaccounted dissipation introduced by regular Voronoi re-partitioning as well as by larger

  18. Ab initio molecular dynamics simulation of the liquid and amorphous structure of Mg65Cu25Gd10 alloy

    International Nuclear Information System (INIS)

    Gao, R.; Zhao, Y.F.; Liu, X.J.; Liu, Z.K.; Hui, X.

    2013-01-01

    The liquid and amorphous structures of Mg 65 Cu 25 Gd 10 alloy were studied by using molecular dynamics methods within the frame of density functional theory. The generalized and partial pair correlation functions, structure factors, coordination numbers and bond pairs for this alloy were analyzed. It is shown that this alloy exhibit typical characterization of liquid structure at the temperature higher than 750 K, and of amorphous structure with shoulders on the second diffuse peaks of the pair correlation functions curves at room temperature. The local short and medium range ordering tends to be increased with the decrease of temperature. Both the liquid and the amorphous structures are mainly composed of icosahedral type of bond pairs. Perfect and distorted icosahedra can be differentiated from the atomic configuration of the amorphous alloy

  19. Static structure, microscopic dynamics and electronic properties of the liquid Bi–Li alloy. An ab initio molecular dynamics study

    International Nuclear Information System (INIS)

    Souto, J; Alemany, M M G; Gallego, L J; González, L E; González, D J

    2013-01-01

    We report an ab initio molecular dynamics study of the static, dynamic and electronic properties of the liquid Bi x Li 1−x alloy, which is a complex binary system with a marked tendency to heterocoordination. The calculated total static structure factors are in good agreement with the available experimental data. The partial dynamic structure factors exhibit side peaks indicative of propagating density fluctuations, and for some concentrations we have found a density fluctuation mode with phase velocity greater than the hydrodynamic sound velocity. We have also evaluated other dynamical properties such as the diffusion coefficients, the shear viscosity and the adiabatic sound velocity. The electronic density of states show that the liquid Bi x Li 1−x alloy has a metallic character, although with strong deviations from the free-electron parabolic curve. The results reported improve the understanding of binary liquid alloys with both fast and slow propagating collective modes. (paper)

  20. Scaling of viscous dynamics in simple liquids

    DEFF Research Database (Denmark)

    Bøhling, Lasse; Ingebrigtsen, Trond; Grzybowski, A.

    2012-01-01

    Supercooled liquids are characterized by relaxation times that increase dramatically by cooling or compression. From a single assumption follows a scaling law according to which the relaxation time is a function of h(ρ) over temperature, where ρ is the density and the function h(ρ) depends on the...

  1. Liquid Structure of CO 2 –Reactive Aprotic Heterocyclic Anion Ionic Liquids from X-ray Scattering and Molecular Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Sheridan, Quintin R.; Oh, Seungmin; Morales-Collazo, Oscar; Castner, Jr., Edward W.; Brennecke, Joan F.; Maginn, Edward J. (Rutgers); (Notre)

    2016-11-23

    A combination of X-ray scattering experiments and molecular dynamics simulations were conducted to investigate the structure of ionic liquids (ILs) which chemically bind CO2. The structure functions were measured and computed for four different ILs consisting of two different phosphonium cations, triethyloctylphosphonium ([P2228]+) and trihexyltetradecylphosphonium ([P66614]+), paired with two different aprotic heterocyclic anions which chemically react with CO2, 2-cyanopyrrolide, and 1,2,4-triazolide. Simulations were able to reproduce the experimental structure functions, and by deconstructing the simulated structure functions, further information on the liquid structure was obtained. All structure functions of the ILs studied had three primary features which have been seen before in other ILs: a prepeak near 0.3–0.4 Å–1 corresponding to polar/nonpolar domain alternation, a charge alternation peak near 0.8 Å–1, and a peak near 1.5 Å–1 due to interactions of adjacent molecules. The liquid structure functions were only mildly sensitive to the specific anion and whether or not they were reacted with CO2. Upon reacting with CO2, small changes were observed in the structure functions of the [P2228]+ ILs, whereas virtually no change was observed upon reacting with CO2 in the corresponding [P66614]+ ILs. When the [P2228]+ cation was replaced with the [P66614]+ cation, there was a significant increase in the intensities of the prepeak and adjacency interaction peak. While many of the liquid structure functions are similar, the actual liquid structures differ as demonstrated by computed spatial distribution functions.

  2. Evaporation of liquid droplets of nano- and micro-meter size as a function of molecular mass and intermolecular interactions: experiments and molecular dynamics simulations.

    Science.gov (United States)

    Hołyst, Robert; Litniewski, Marek; Jakubczyk, Daniel

    2017-09-13

    Transport of heat to the surface of a liquid is a limiting step in the evaporation of liquids into an inert gas. Molecular dynamics (MD) simulations of a two component Lennard-Jones (LJ) fluid revealed two modes of energy transport from a vapour to an interface of an evaporating droplet of liquid. Heat is transported according to the equation of temperature diffusion, far from the droplet of radius R. The heat flux, in this region, is proportional to temperature gradient and heat conductivity in the vapour. However at some distance from the interface, Aλ, (where λ is the mean free path in the gas), the temperature has a discontinuity and heat is transported ballistically i.e. by direct individual collisions of gas molecules with the interface. This ballistic transport reduces the heat flux (and consequently the mass flux) by the factor R/(R + Aλ) in comparison to the flux obtained from temperature diffusion. Thus it slows down the evaporation of droplets of sizes R ∼ Aλ and smaller (practically for sizes from 10 3 nm down to 1 nm). We analyzed parameter A as a function of interactions between molecules and their masses. The rescaled parameter, A(k B T b /ε 11 ) 1/2 , is a linear function of the ratio of the molecular mass of the liquid molecules to the molecular mass of the gas molecules, m 1 /m 2 (for a series of chemically similar compounds). Here ε 11 is the interaction parameter between molecules in the liquid (proportional to the enthalpy of evaporation) and T b is the temperature of the gas in the bulk. We tested the predictions of MD simulations in experiments performed on droplets of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. They were suspended in an electrodynamic trap and evaporated into dry nitrogen gas. A changes from ∼1 (for ethylene glycol) to approximately 10 (for tetraethylene glycol) and has the same dependence on molecular parameters as obtained for the LJ fluid in MD simulations. The value of x = A

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

    Science.gov (United States)

    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.

  4. Molecular and Thermodynamic Properties of Zwitterions versus Ionic Liquids: A Comprehensive Computational Analysis to Develop Advanced Separation Processes.

    Science.gov (United States)

    Moreno, Daniel; Gonzalez-Miquel, Maria; Ferro, Victor R; Palomar, Jose

    2018-04-05

    Zwitterion ionic liquids (ZIs) are compounds in which both counterions are covalently tethered, conferring them with unique characteristics; however, most of their properties are still unknown, representing a bottleneck to exploit their practical applications. Herein, the molecular and fluid properties of ZIs and their mixtures were explored by means of quantum chemical analysis based on the density functional theory (DFT) and COSMO-RS method, and compared against homologous ionic liquids (ILs) to provide a comprehensive overview of the effect of the distinct structures on their physicochemical and thermodynamic behavior. Overall, ZIs were revealed as compounds with higher polarity and stronger hydrogen-bonding capacity, implying higher density, viscosity, melting point, and even lower volatility than structurally similar ILs. The phase equilibrium of binary and ternary systems supports stronger attractive interactions between ZIs and polar compounds, whereas higher liquid-liquid immiscibility with nonpolar compounds may be expected. Ultimately, the performance of ZIs in the wider context of separation processes is illustrated, while providing molecular insights to allow their selection and design for relevant applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Effect of Molecular Weight on the Properties of Liquid Epoxidized Natural Rubber Acrylate (LENRA)/ Silica Hybrid Composites

    International Nuclear Information System (INIS)

    Eda Yuhana Ariffin; Azizan Ahmad; Dahlan Mohd; Mahathir Mohamed

    2011-01-01

    This paper reports on the effect of molecular weight on the morphological and mechanical properties of liquid epoxidized natural rubber acrylate (LENRA)/ silica hybrid composites prepared by sol-gel technique. The sol-gel reaction was conducted at different concentration of tetraethyl orthosilicate (TEOS), used as a precursor of silica. TEOS were introduced in 10, 20, 30, 40 and 50 parts per hundred rubber (phr) in the composites. Two different molecular weights of ENR were used to study the effect of molecular weight on the mechanical and morphological properties of the compounds. These compounds were cured by ultraviolet (UV) irradiation. The mechanical properties were studied through pendulum hardness and scratch tests. Higher molecular weight of ENR showed better mechanical properties than lower molecular weight. Transmission electron microscope was used to determine the silica size and to study the distribution and dispersion of the silica particles. High molecular weight showed greater distribution and dispersion of silica particles with diameter of 13 - 256 nm. Morphological and mechanical properties of LENRA/ silica hybrid composites were improved by using high molecular weight of ENR. (author)

  6. Transient molecular orientation and rheology in flow aligning thermotropic liquid crystalline polymers

    International Nuclear Information System (INIS)

    Ugaz, Victor M.; Burghardt, Wesley R.; Zhou, Weijun; Kornfield, Julia A.

    2001-01-01

    Quantitative measurements of molecular orientation and rheology are reported for various transient shear flows of a nematic semiflexible copolyether. Unlike the case of lyotropic liquid crystalline polymers (LCPs), whose structure and rheology in shear are dominated by director tumbling, this material exhibits flow aligning behavior. The observed behavior is quite similar to that seen in a copolyester that we have recently studied [Ugaz and Burghardt (1998)], suggesting that flow aligning dynamics may predominate in main-chain thermotropes that incorporate significant chain flexibility. Since the flow aligning regime has received little attention in previous attempts to model the rheology of textured, polydomain LCPs, we attempt to determine whether available models are capable of predicting the orientation and stress response of this class of LCP. We first examine the predictions of the polydomain Ericksen model, an adaptation of Ericksen's transversely isotropic fluid model which accounts for the polydomain distribution of director orientation while neglecting distortional elasticity. This simple model captures a number of qualitative and quantitative features associated with the evolution of orientation and stress during shear flow inception, but cannot cope with reversing flows. To consider the possible role of distortional elasticity in the re-orientation dynamics upon reversal, we evaluate the mesoscopically averaged domain theory of Larson and Doi [Larson and Doi (1991)], which incorporates a phenomenological description of distortional elastic effects. To date, their approach to account for polydomain structure has only been applied to describe tumbling LCPs. We find that it captures the qualitative transient orientation response to flow reversals, but is less successful in describing the evolution of stresses. This is linked to the decoupling approximation adopted during the model's development. Finally, a modified polydomain Ericksen model is introduced

  7. Synthesis and Supramolecular Chemistry of Novel Liquid Crystalline Crown Ether-Substituted Phthalocyanines : Toward Molecular Wires and Molecular Ionoelectronics

    NARCIS (Netherlands)

    Nostrum, Cornelus F. van; Picken, Stephen J.; Schouten, Arend-Jan; Nolte, Roeland J.M.

    1995-01-01

    The synthesis of the metal-free and the dihydroxysilicon derivatives of tetrakis[4’,5’-bis(decoxy)benzo-18-crown-6]phthalocyanine is described. The metal-free phthalocyanine is liquid crystalline and exhibits a crystalline phase to mesophase transition at 148 °C. The structures of the crystalline

  8. Supercooling release of micro-size water droplets on microporous surfaces with cooling

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chun Wan; Kang, Chae Dong [Chonbuk National University, Jeonju (Korea, Republic of)

    2012-06-15

    The gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells plays a key role in controlling moisture in these cells. When the GDL is exposed to a cold environment, the water droplets or water nets in the GDL freeze. This work observed the supercooling and freezing behaviors of water droplets under low temperature. A GDL made of carbon fiber was coated with a waterproof material with 0%, 40%, and 60% PTFE (polytetrafluoroethylene) contents. The cooling process was investigated according to temperature, and the water droplets on the GDL were supercooled and frozen. Delay in the supercooling release was correlated with the size of water droplets on the GDL and the coating rate of the layer. Moreover, the supercooling degree of the droplets decreased as the number of freeze thaw cycles in the GDL increased.

  9. In search of invariants for viscous liquids in the density scaling regime: investigations of dynamic and thermodynamic moduli.

    Science.gov (United States)

    Jedrzejowska, Agnieszka; Grzybowski, Andrzej; Paluch, Marian

    2017-07-19

    In this paper, we report the nontrivial results of our investigations of dynamic and thermodynamic moduli in search of invariants for viscous liquids in the density scaling regime by using selected supercooled van der Waals liquids as representative materials. Previously, the dynamic modulus M p-T (defined in the pressure-temperature representation by the ratio of isobaric activation energy and activation volume) as well as the ratio B T /M p-T (where B T is the thermodynamic modulus defined as the inverse isothermal compressibility) have been suggested as some kinds of material constants. We have established that they are not valid in the explored wide range of temperatures T over a dozen decades of structural relaxation times τ. The temperature dependences of M p-T and B T /M p-T have been elucidated by comparison with the well-known measure of the relative contribution of temperature and density fluctuations to molecular dynamics near the glass transition, i.e., the ratio of isochoric and isobaric activation energies. Then, we have implemented an idea to transform the definition of the dynamic modulus M p-T from the p-T representation to the V-T one. This idea relied on the disentanglement of combined temperature and density fluctuations involved in isobaric parameters and has resulted in finding an invariant for viscous liquids in the density scaling regime, which is the ratio of thermodynamic and dynamic moduli, B T /M V-T . In this way, we have constituted a characteristic of thermodynamics and molecular dynamics, which remains unchanged in the supercooled liquid state for a given material, the molecular dynamics of which obeys the power density scaling law.

  10. Nanoscale liquid interfaces wetting, patterning and force microscopy at the molecular scale

    CERN Document Server

    Ondarçuhu, Thierry

    2013-01-01

    This book addresses the recent developments in the investigation and manipulation of liquids at the nanoscale. This new field has shown important breakthroughs on the basic understanding of physical mechanisms involving liquid interfaces, which led to applications in nanopatterning. It has also consequences in force microscopy imaging in liquid environment. The book proposes is a timely review of these various aspects. It is co-authored by 25 among the most prominent scientists in the field.

  11. Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics.

    Science.gov (United States)

    Tanzi, Luana; Ramondo, Fabio; Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo

    2015-09-21

    We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.

  12. Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Tanzi, Luana; Ramondo, Fabio, E-mail: fabio.ramondo@univaq.it [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, L’Aquila I-67100 (Italy); Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo, E-mail: lorenzo.gontrani@uniroma1.it [Department of Chemistry, University of Rome ‘La Sapienza’, P.le Aldo Moro 5, I-00185 Rome (Italy)

    2015-09-21

    We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.

  13. Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics

    International Nuclear Information System (INIS)

    Tanzi, Luana; Ramondo, Fabio; Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo

    2015-01-01

    We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features

  14. Inulin in Medicinal Plants (IV) : Reversed-Phase High-Performance Liquid Chromatography of Inulin after Acetylation : Molecular-Weight Distribution of Inulin in Medicinal Plants

    OpenAIRE

    三野, 芳紀; 筒井, 聡美; 太田, 長世; YOSHIKI, MINO; SATOMI, TSUTSUI; NAGAYO, OTA; 大阪薬科大学; 大阪薬科大学; 大阪薬科大学; Osaka College of Pharmacy; Osaka College of Pharmacy; Osaka College of Pharmacy

    1985-01-01

    Reversed-phase high-performance liquid chromatography coupled with pre-acetylation enabled acculate molecular-weight assay of inulin in medicinal plants to be conducted. The results clearly showed that the molecular-weight distribution of inulin varied depending on the stage of growth: Small molecular weight inulin polymers were detected in large quantity in the earlier growth stage whereas large molecular weight inulin polymers at the flowering and post flowering period.

  15. Effect of freeze-thaw repetitions upon the supercooling release ability of ice-nucleating bacteria

    International Nuclear Information System (INIS)

    Tsuchiya, Yooko; Hasegawa, Hiromi; Sasaki, Kazuhiro

    2004-01-01

    We have studied the durability of ice-nucleating bacteria with a potent supercooling release capacity through repeated freeze-thaw cycles. Through experiment, we confirmed that UV sterilized Erwinia ananas maintains a superior supercooling release capacity at around -1degC through 2000 freeze-thaw cycles. We also found that γ-ray sterilization, which is more suitable than UV for large-scale sterilization treatment, has a similar effect at appropriately selected doses. (author)

  16. Substrate and surfactant effects on the glass-liquid transition of thin water films.

    Science.gov (United States)

    Souda, Ryutaro

    2006-09-07

    Temperature-programmed time-of-flight secondary ion mass spectrometry (TP-TOF-SIMS) and temperature-programmed desorption (TPD) have been used to perform a detailed investigation of the adsorption, desorption, and glass-liquid transition of water on the graphite and Ni(111) surfaces in the temperature range 13-200 K. Water wets the graphite surface at 100-120 K, and the hydrogen-bonded network is formed preferentially in the first monolayer to reduce the number of nonbonding hydrogens. The strongly chemisorbed water molecules at the Ni(111) surface do not form such a network and play a role in stabilizing the film morphology up to 160 K, where dewetting occurs abruptly irrespective of the film thickness. The surface structure of the water film formed on graphite is fluctuated considerably, resulting in deweting at 150-160 K depending on the film thickness. The dewetted patches of graphite are molecularly clean, whereas the chemisorbed water remains on the Ni(111) surface even after evaporation of the film. The abrupt drop in the desorption rate of water molecules at 160 K, which has been attributed to crystallization in the previous TPD studies, is found to disappear completely when a monolayer of methanol is present on the surface. This is because the morphology of supercooled liquid water is changed by the surface tension, and it is quenched by termination of the free OH groups on the surface. The surfactant methanol desorbs above 160 K since the hydrogen bonds of the water molecules are reconstructed. The drastic change in the properties of supercooled liquid water at 160 K should be ascribed to the liquid-liquid phase transition.

  17. Controlled Sol-Gel Transitions of a Thermoresponsive Polymer in a Photoswitchable Azobenzene Ionic Liquid as a Molecular Trigger.

    Science.gov (United States)

    Wang, Caihong; Hashimoto, Kei; Tamate, Ryota; Kokubo, Hisashi; Watanabe, Masayoshi

    2018-01-02

    Producing ionic liquids (ILs) that function as molecular trigger for macroscopic change is a challenging issue. Photoisomerization of an azobenzene IL at the molecular level evokes a macroscopic response (light-controlled mechanical sol-gel transitions) for ABA triblock copolymer solutions. The A endblocks, poly(2-phenylethyl methacrylate), show a lower critical solution temperature in the IL mixture containing azobenzene, while the B midblock, poly(methyl methacrylate), is compatible with the mixture. In a concentrated polymer solution, different gelation temperatures were observed in it under dark and UV conditions. Light-controlled sol-gel transitions were achieved by a photoresponsive solubility change of the A endblocks upon photoisomerization of the azobenzene IL. Therefore, an azobenzene IL as a molecular switch can tune the self-assembly of a thermoresponsive polymer, leading to macroscopic light-controlled sol-gel transitions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Computer simulations of supercooled polymer melts in the bulk and in confined geometry

    International Nuclear Information System (INIS)

    Baschnagel, J; Varnik, F

    2005-01-01

    We survey results of computer simulations for the structure and dynamics of supercooled polymer melts and films. Our survey is mainly concerned with features of a coarse grained polymer model-a bead-spring model-in the temperature regime above the critical glass temperature T c of the ideal mode-coupling theory (MCT). We divide our discussion into two parts: a part devoted to bulk properties and a part dealing with thin films. The discussion of the bulk properties focuses on two aspects: a comparison of the simulation results with MCT and an analysis of dynamic heterogeneities. We explain in detail how the analyses are performed and what results may be obtained, and we critically assess their strengths and weaknesses. In discussing the application of MCT we also present first results of a quantitative comparison which does not rely on fits, but exploits static input from the simulation to predict the relaxation dynamics. The second part of this review is devoted to extensions of the simulations from the bulk to thin films. We explore in detail the influence of the boundary condition, imposed by smooth or rough walls, on the structure and dynamics of the polymer melt. Geometric confinement is found to shift the glass transition temperature T g (or T c in our case) relative to the bulk. We compare our and other simulation results for the T g shift with experimental data, briefly survey some theoretical ideas for explaining these shifts and discuss related simulation work on the glass transition of confined liquids. Finally, we also present some technical details of how to perform fits to MCT and give a brief introduction to another approach to the glass transition based on the potential energy landscape of a liquid. (topical review)

  19. Modified free volume theory of self-diffusion and molecular theory of shear viscosity of liquid carbon dioxide.

    Science.gov (United States)

    Nasrabad, Afshin Eskandari; Laghaei, Rozita; Eu, Byung Chan

    2005-04-28

    In previous work on the density fluctuation theory of transport coefficients of liquids, it was necessary to use empirical self-diffusion coefficients to calculate the transport coefficients (e.g., shear viscosity of carbon dioxide). In this work, the necessity of empirical input of the self-diffusion coefficients in the calculation of shear viscosity is removed, and the theory is thus made a self-contained molecular theory of transport coefficients of liquids, albeit it contains an empirical parameter in the subcritical regime. The required self-diffusion coefficients of liquid carbon dioxide are calculated by using the modified free volume theory for which the generic van der Waals equation of state and Monte Carlo simulations are combined to accurately compute the mean free volume by means of statistical mechanics. They have been computed as a function of density along four different isotherms and isobars. A Lennard-Jones site-site interaction potential was used to model the molecular carbon dioxide interaction. The density and temperature dependence of the theoretical self-diffusion coefficients are shown to be in excellent agreement with experimental data when the minimum critical free volume is identified with the molecular volume. The self-diffusion coefficients thus computed are then used to compute the density and temperature dependence of the shear viscosity of liquid carbon dioxide by employing the density fluctuation theory formula for shear viscosity as reported in an earlier paper (J. Chem. Phys. 2000, 112, 7118). The theoretical shear viscosity is shown to be robust and yields excellent density and temperature dependence for carbon dioxide. The pair correlation function appearing in the theory has been computed by Monte Carlo simulations.

  20. Absorption Refrigeration Cycles with Ammonia-Ionic Liquid Working Pairs Studied by Molecular Simulation

    NARCIS (Netherlands)

    Becker, T.M.; Wang, M.; Kabra, Abhishek; Jamali, S.H.; Ramdin, M.; Dubbeldam, D.; Infante Ferreira, C.A.; Vlugt, T.J.H.

    2018-01-01

    For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an

  1. Effect of Molecular Flexibility on the Nematic-to-Isotropic Phase Transition for Highly Biaxial Molecular Non-Symmetric Liquid Crystal Dimers

    Science.gov (United States)

    Sebastián, Nerea; López, David Orencio; Diez-Berart, Sergio; de la Fuente, María Rosario; Salud, Josep; Pérez-Jubindo, Miguel Angel; Ros, María Blanca

    2011-01-01

    In this work, a study of the nematic (N)–isotropic (I) phase transition has been made in a series of odd non-symmetric liquid crystal dimers, the α-(4-cyanobiphenyl-4’-yloxy)-ω-(1-pyrenimine-benzylidene-4’-oxy) alkanes, by means of accurate calorimetric and dielectric measurements. These materials are potential candidates to present the elusive biaxial nematic (NB) phase, as they exhibit both molecular biaxiality and flexibility. According to the theory, the uniaxial nematic (NU)–isotropic (I) phase transition is first-order in nature, whereas the NB–I phase transition is second-order. Thus, a fine analysis of the critical behavior of the N–I phase transition would allow us to determine the presence or not of the biaxial nematic phase and understand how the molecular biaxiality and flexibility of these compounds influences the critical behavior of the N–I phase transition. PMID:28824100

  2. Thermophysical properties of imidazolium tricyanomethanide ionic liquids: experiments and molecular simulation.

    Science.gov (United States)

    Zubeir, Lawien F; Rocha, Marisa A A; Vergadou, Niki; Weggemans, Wilko M A; Peristeras, Loukas D; Schulz, Peter S; Economou, Ioannis G; Kroon, Maaike C

    2016-08-17

    The low-viscous tricyanomethanide ([TCM](-))-based ionic liquids (ILs) are gaining increasing interest as attractive fluids for a variety of industrial applications. The thermophysical properties (density, viscosity, surface tension, electrical conductivity and self-diffusion coefficient) of the 1-alkyl-3-methylimidazolium tricyanomethanide [Cnmim][TCM] (n = 2, 4 and 6-8) IL series were experimentally measured over the temperature range from 288 to 363 K. Moreover, a classical force field optimized for the imidazolium-based [TCM](-) ILs was used to calculate their thermodynamic, structural and transport properties (density, surface tension, self-diffusion coefficients, viscosity) in the temperature range from 300 to 366 K. The predictions were directly compared against the experimental measurements. The effects of anion and alkyl chain length on the structure and thermophysical properties have been evaluated. In cyano-based ILs, the density decreases with increasing molar mass, in contrast to the behavior of the fluorinated anions, being in agreement with the literature. The contribution per -CH2- group to the increase of the viscosity presents the following sequence: [PF6](-) > [BF4](-) > [Tf2N](-) > [DCA](-) > [TCB](-) > [TCM](-). [TCM](-)-based ILs show lower viscosity than dicyanamide ([DCA](-))- and tetracyanoborate ([TCB](-))-based ILs, while the latter two exhibit a crossover which depends both on temperature and the alkyl chain length of the cation. The surface tension of the investigated ILs decreases with increasing alkyl chain length. [C2mim][TCM] shows an outlier behavior compared to other members of the homologous series. The surface enthalpies and surface entropies for all the studied systems have been calculated based on the experimentally determined surface tensions. The relationship between molar conductivity and viscosity was analyzed using the Walden rule. The experimentally determined self-diffusion coefficients of the cations are in good

  3. Melting of superheated molecular crystals

    Science.gov (United States)

    Cubeta, Ulyana; Bhattacharya, Deepanjan; Sadtchenko, Vlad

    2017-07-01

    Melting dynamics of micrometer scale, polycrystalline samples of isobutane, dimethyl ether, methyl benzene, and 2-propanol were investigated by fast scanning calorimetry. When films are superheated with rates in excess of 105 K s-1, the melting process follows zero-order, Arrhenius-like kinetics until approximately half of the sample has transformed. Such kinetics strongly imply that melting progresses into the bulk via a rapidly moving solid-liquid interface that is likely to originate at the sample's surface. Remarkably, the apparent activation energies for the phase transformation are large; all exceed the enthalpy of vaporization of each compound and some exceed it by an order of magnitude. In fact, we find that the crystalline melting kinetics are comparable to the kinetics of dielectric α-relaxation in deeply supercooled liquids. Based on these observations, we conclude that the rate of non-isothermal melting for superheated, low-molecular-weight crystals is limited by constituent diffusion into an abnormally dense, glass-like, non-crystalline phase.

  4. Towards Molecular Characterization of Mineral-Organic Matter Interface Using In Situ Liquid Secondary Ion Mass Spectrometry

    Science.gov (United States)

    Zhu, Z.; Yu, X. Y.

    2017-12-01

    Organo-Mineral-Microbe interactions in terrestrial ecosystems are of great interest. Quite a few models have been developed through extensive efforts in this field. However, predictions from current models are far from being accurate, and many debates still exist. One of the major reasons is that most experimental data generated from bulk analysis, and the information of molecular dynamics occurring at mineral-organic matter interface is rare. Such information has been difficult to obtain, due to lack of suitable in situ analysis tools. Recently, we have developed in situ liquid secondary ion mass spectrometry (SIMS) at Pacific Northwest National Laboratory1, and it has shown promise to provide both elemental and molecular information at vacuum-liquid and solid-liquid interfaces.2 In this presentation, we demonstrate that in situ liquid SIMS can provide critical molecular information at solid substrate-live biofilm interface.3 Shewanella oneidensis is used as a model micro-organism and silicon nitride as a model mineral surface. Of particular interest, biologically relevant water clusters have been first observed in the living biofilms. Characteristic fragments of biofilm matrix components such as proteins, polysaccharides, and lipids can be molecularly examined. Furthermore, characteristic fatty acids (e.g., palmitic acid), quinolone signal, and riboflavin fragments were found to respond after the biofilm is treated with Cr(VI), leading to biofilm dispersal. Significant changes in water clusters and quorum sensing signals indicative of intercellular communication in the aqueous environment were observed, suggesting that they might result in fatty acid synthesis and inhibition of riboflavin production. The Cr(VI) reduction seems to follow the Mtr pathway leading to Cr(III) formation. Our approach potentially opens a new avenue for in-situ understanding of mineral-organo or mineral-microbe interfaces using in situ liquid SIMS and super resolution fluorescence

  5. A Molecular Dynamics-Quantum Mechanics Theoretical Study of DNA-Mediated Charge Transport in Hydrated Ionic Liquids.

    Science.gov (United States)

    Meng, Zhenyu; Kubar, Tomas; Mu, Yuguang; Shao, Fangwei

    2018-05-08

    Charge transport (CT) through biomolecules is of high significance in the research fields of biology, nanotechnology, and molecular devices. Inspired by our previous work that showed the binding of ionic liquid (IL) facilitated charge transport in duplex DNA, in silico simulation is a useful means to understand the microscopic mechanism of the facilitation phenomenon. Here molecular dynamics simulations (MD) of duplex DNA in water and hydrated ionic liquids were employed to explore the helical parameters. Principal component analysis was further applied to capture the subtle conformational changes of helical DNA upon different environmental impacts. Sequentially, CT rates were calculated by a QM/MM simulation of the flickering resonance model based upon MD trajectories. Herein, MD simulation illustrated that the binding of ionic liquids can restrain dynamic conformation and lower the on-site energy of the DNA base. Confined movement among the adjacent base pairs was highly related to the increase of electronic coupling among base pairs, which may lead DNA to a CT facilitated state. Sequentially combining MD and QM/MM analysis, the rational correlations among the binding modes, the conformational changes, and CT rates illustrated the facilitation effects from hydrated IL on DNA CT and supported a conformational-gating mechanism.

  6. Molecular dynamics studies and quantification of the effect of chirality on the formation of liquid crystal mesophases

    International Nuclear Information System (INIS)

    Solymosi, Miklos

    2002-01-01

    Results are presented from theoretical studies and from a series of molecular dynamics simulations undertaken to quantify the effect of chirality on the formation of liquid crystal mesophases. In the theoretical studies we have proposed a scaled chiral index with a formulation which allows comparison to be made between molecules comprising different numbers of atoms. We have undertaken chirality calculations utilizing the proposed scaled chiral index, G 0S , for one optimized static molecular geometry for a range of liquid crystal chiral dopants and ferroelectric liquid crystal molecules. The scaled chiral index, G 0S , allows a rapid calculation to be made of a pseudoscalar quantity which shows a good correlation with the helical twisting power of liquid crystal chiral dopants in a nematic liquid crystal solvent. This could prove a powerful aid in the design of novel dopant molecules where the dopant is rigid and the helical twisting is predominantly a steric effect. The same scaled chirality index, G 0S , calculation for ferroelectric liquid crystal molecules hints at an inverse correlation with spontaneous polarization agreeing with some experimental results. The scaled chiral index is a chemically useful index that can also be decomposed into atomic or functional group contributions, thereby creating a new measure of the asymmetric potential of functional groups and their different possible substitution positions. In the molecular dynamics simulation studies we have investigated two three-site Gay-Berne models, one chiral and the other achiral, each with a rotated central site forming a zigzag shape. In the chiral model one of the end site was additionally rotated out of the plane of the other two sites by a chiral angle θ c . Results from the achiral phase simulations support the theory that steric molecular shape can be associated with a driving force that leads to the smectic A - smectic C phase transition since such a transition was observed in the achiral

  7. Path integral molecular dynamics within the grand canonical-like adaptive resolution technique: Simulation of liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Animesh, E-mail: animesh@zedat.fu-berlin.de; Delle Site, Luigi, E-mail: dellesite@fu-berlin.de [Institute for Mathematics, Freie Universität Berlin, Berlin (Germany)

    2015-09-07

    Quantum effects due to the spatial delocalization of light atoms are treated in molecular simulation via the path integral technique. Among several methods, Path Integral (PI) Molecular Dynamics (MD) is nowadays a powerful tool to investigate properties induced by spatial delocalization of atoms; however, computationally this technique is very demanding. The above mentioned limitation implies the restriction of PIMD applications to relatively small systems and short time scales. One of the possible solutions to overcome size and time limitation is to introduce PIMD algorithms into the Adaptive Resolution Simulation Scheme (AdResS). AdResS requires a relatively small region treated at path integral level and embeds it into a large molecular reservoir consisting of generic spherical coarse grained molecules. It was previously shown that the realization of the idea above, at a simple level, produced reasonable results for toy systems or simple/test systems like liquid parahydrogen. Encouraged by previous results, in this paper, we show the simulation of liquid water at room conditions where AdResS, in its latest and more accurate Grand-Canonical-like version (GC-AdResS), is merged with two of the most relevant PIMD techniques available in the literature. The comparison of our results with those reported in the literature and/or with those obtained from full PIMD simulations shows a highly satisfactory agreement.

  8. Molecular dynamics of liquid alkaline-earth metals near the melting ...

    Indian Academy of Sciences (India)

    Results of the studies of the properties like binding energy, the pair distrib- ... of the pseudopotential used from solid to liquid environment in the case of .... In this expression, Eeg represents the ground state energy of the electron gas, for.

  9. Characterisation of uremic "Middle molecular"fractions by gas chromatography mass spectrometry, isotachophoresis, and liquid chromatography

    NARCIS (Netherlands)

    Schoots, A.C.; Mikkers, F.E.P.; Claessens, H.A.; Smet, de R.; Landschoot, van N.; Ringoir, S.M.G.

    1982-01-01

    Uremic ultrafiltrates (and normal serum, for comparison) were fractionated by means of gel filtration. The collected fractions were further investigated by combined analytical techniques: "high- performance" liquid chromatography, gas chromatography, mass spectrometry, and isotachophoresis.

  10. Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub-Nanoporous Materials.

    Science.gov (United States)

    Sakamoto, Takeshi; Ogawa, Takafumi; Nada, Hiroki; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro; Henmi, Masahiro; Kato, Takashi

    2018-01-01

    Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self-organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self-organized sub-nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub-nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability.

  11. Ultrahigh-throughput exfoliation of graphite into pristine ‘single-layer’ graphene using microwaves and molecularly engineered ionic liquids

    Science.gov (United States)

    Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

    2015-09-01

    Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards ‘single-layer’ graphene (that is, with thicknesses oligomeric ionic liquids up to ~100 mg ml-1, and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

  12. Supercooling and cold energy storage characteristics of nano-media in ball-packed porous structures

    Directory of Open Access Journals (Sweden)

    Zhao Qunzhi

    2015-04-01

    Full Text Available The presented experiments aimed to study the supercooling and cold-energy storage characteristics of nanofluids and water-based nano-media in ball-packed porous structures (BPS. Titanium dioxide nanoparticles (TiO2 NPs measuring 20nm and 80nm were used as additives and sodium dodecyl benzene sulphonate (SDBS was used as anionic surfactant. The experiments used different concentrations of nanofluid, distilled with BPS of different spherical diameter and different concentrations of nano-media, and were conducted 20 times. Experimental results of supercooling were analysed by statistical methods. Results show that the average and peak supercooling degrees of nanofluids and nano-media in BPS are lower than those of distilled water. For the distilled water in BPS, the supercooling degree decreases on the whole with the decrease of the ball diameter. With the same spherical diameter (8mm of BPS, the supercooling degree of TiO2 NPs measuring 20nm is lower than the supercooling degree of distilled water in BPS. Step-cooling experiments of different concentrations of nanofluids and nano-media in BPS were also conducted. Results showed that phase transition time is reduced because of the presence of TiO2 NPs. The BPS substrate and the NPs enhance the heat transfer. Distilled water with a porous solid base and nanoparticles means the amount of cold-energy storage increases and the supercooling degree and the total time are greatly reduced. The phase transition time of distilled water is about 3.5 times that of nano-media in BPS.

  13. Thermophysical properties of liquid UO2, ZrO2 and corium by molecular dynamics and predictive models

    International Nuclear Information System (INIS)

    Kim, Woong Kee; Shim, Ji Hoon; Kaviany Massoud

    2016-01-01

    The analysis of such accidents (fate of the melt), requires accurate corium thermophysical properties data up to 5000 K. In addition, the initial corium melt superheat melt, determined from such properties, are key in predicting the fuel-coolant interactions (FCIs) and convection and retention of corium in accident scenarios, e.g., core-melt down corium discharge from reactor pressure vessels and spreading in external core-catcher. Due to the high temperatures, data on molten corium and its constituents are limited, so there are much data scatters and mostly extrapolations (even from solid state) have been used. Here we predict the thermophysical properties of molten UO 2 and ZrO 2 using classical molecular dynamics (MD) simulations (properties of corium are predicted using the mixture theories and UO 2 and ZrO 2 properties). The thermophysical properties (density, compressibility, heat capacity, viscosity and surface tension) of liquid UO 2 and ZrO 2 are predicted using classical molecular dynamics simulations, up to 5000 K. For atomic interactions, the CRG and the Teter potential models are found most appropriate. The liquid behavior is verified with the random motion of the constituent atoms and the pair-distribution functions, starting with the solid phase and raising the temperature to realize liquid phase. The viscosity and thermal conductivity are calculated with the Green-Kubo autocorrelation decay formulae and compared with the predictive models of Andrade and Bridgman. For liquid UO 2 , the CRG model gives satisfactory MD predictions. For ZrO 2 , the density is reliably predicted with the CRG potential model, while the compressibility and viscosity are more accurately predicted by the Teter model

  14. Three-site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2-supported Ziegler-Natta catalyst

    NARCIS (Netherlands)

    Shimizu, Fumihiko; Pater, J.T.M.; Weickert, G.

    2001-01-01

    This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl2-supported catalyst is used in a liquid pool polymerization at constant H2 concentration and temperature. To track the

  15. Orbital free ab initio molecular dynamics simulation study of some static and dynamic properties of liquid noble metals

    Directory of Open Access Journals (Sweden)

    G.M. Bhuiyan

    2012-10-01

    Full Text Available Several static and dynamic properties of liquid Cu, Ag and Au at thermodynamic states near their respective melting points, have been evaluated by means of the orbital free ab-initio molecular dynamics simulation method. The calculated static structure shows good agreement with the available X-ray and neutron diffraction data. As for the dynamic properties, the calculated dynamic structure factors point to the existence of collective density excitations along with a positive dispersion for l-Cu and l-Ag. Several transport coefficients have been obtained which show a reasonable agreement with the available experimental data.

  16. On the density scaling of pVT data and transport properties for molecular and ionic liquids.

    Science.gov (United States)

    López, Enriqueta R; Pensado, Alfonso S; Fernández, Josefa; Harris, Kenneth R

    2012-06-07

    In this work, a general equation of state (EOS) recently derived by Grzybowski et al. [Phys. Rev. E 83, 041505 (2011)] is applied to 51 molecular and ionic liquids in order to perform density scaling of pVT data employing the scaling exponent γ(EOS). It is found that the scaling is excellent in most cases examined. γ(EOS) values range from 6.1 for ammonia to 13.3 for the ionic liquid [C(4)C(1)im][BF(4)]. These γ(EOS) values are compared with results recently reported by us [E. R. López, A. S. Pensado, M. J. P. Comuñas, A. A. H. Pádua, J. Fernández, and K. R. Harris, J. Chem. Phys. 134, 144507 (2011)] for the scaling exponent γ obtained for several different transport properties, namely, the viscosity, self-diffusion coefficient, and electrical conductivity. For the majority of the compounds examined, γ(EOS) > γ, but for hexane, heptane, octane, cyclopentane, cyclohexane, CCl(4), dimethyl carbonate, m-xylene, and decalin, γ(EOS) liquids. For viscosities and the self-diffusion coefficient-temperature ratio, we have tested the relation linking EOS and dynamic scaling parameters, proposed by Paluch et al. [J. Phys. Chem. Lett. 1, 987-992 (2010)] and Grzybowski et al. [J. Chem. Phys. 133, 161101 (2010); Phys. Rev. E 82, 013501 (2010)], that is, γ = (γ(EOS)/φ) + γ(G), where φ is the stretching parameter of the modified Avramov relation for the density scaling of a transport property, and γ(G) is the Grüneisen constant. This relationship is based on data for structural relaxation times near the glass transition temperature for seven molecular liquids, including glass formers, and a single ionic liquid. For all the compounds examined in our much larger database the ratio (γ(EOS)/φ) is actually higher than γ, with the only exceptions of propylene carbonate and 1-methylnaphthalene. Therefore, it seems the relation proposed by Paluch et al. applies only in certain cases, and is really not generally applicable to liquid transport properties such as

  17. Full molecular dynamics simulations of liquid water and carbon tetrachloride for two-dimensional Raman spectroscopy in the frequency domain

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Ju-Yeon, E-mail: ju8879@kuchem.kyoto-u.ac.jp; Ito, Hironobu, E-mail: h.ito@kuchem.kyoto-u.ac.jp; Tanimura, Yoshitaka, E-mail: tanimura@kuchem.kyoto-u.ac.jp

    2016-12-20

    Frequency-domain two-dimensional (2D) Raman signals, which are equivalent to coherent two-dimensional Raman scattering (COTRAS) signals, for liquid water and carbon tetrachloride were calculated using an equilibrium–nonequilibrium hybrid molecular dynamics (MD) simulation algorithm. An appropriate representation of the 2D Raman spectrum obtained from MD simulations provides an easy-to-understand depiction of structural and dynamical properties. We elucidate mechanisms governing the 2D signal profiles involving anharmonic mode–mode coupling and the nonlinearities of the polarizability for the intermolecular and intramolecular vibrational modes. The predicted signal profiles and intensities can be utilized to analyze recently developed single-beam 2D spectra, whose signals are generated from a coherently controlled pulse, allowing the single-beam measurement to be carried out more efficiently. Moreover, the MD simulation results allow us to visualize the molecular structure and dynamics by comparing the accurately calculated spectrum with experimental result.

  18. Selective separation of uranium from nuclear waste solution by bis (2,4,4-trimethylpentyl phosphinic) acid in ionic liquid and molecular diluents: a comparative study

    International Nuclear Information System (INIS)

    Singh, Manpreet; Sengupta, Arijit; Murali, M.S.; Adya, V.C.; Kadam, R.M.

    2016-01-01

    Room temperature ionic liquid has been world-wide considered as the potential 'green' alternatives to the molecular diluents. A comparative study was carried out for studying selective separation of uranium from radioactive waste solution using Bis(2,4,4-trimethylpentyl phosphinic) acid in molecular diluent (xylene) and ionic liquid (C 8 mimNTf 2 ). For ionic liquid based system, the extraction kinetics was found to be slower compared to the molecular diluents. This was attributed to the higher viscosity of ionic liquid. In ionic liquid the extraction occurs with the predominance of 'ion exchange' mechanism through (UO 2 (NO 3 ). 2L) + species, while for xylene based system 'solvation' mechanism predominates at higher feed acidity. The extraction process in ionic liquid was found to be thermodynamically more favoured than in xylene. The nature of the extracted species was found to be different in ionic liquid and xylene as obtained from difference in luminescence emission profiles and lifetime of the extracted complex. Ionic liquid based system was found to be radiolytically more stable than the molecular diluents based solvent system. Na 2 CO 3 solution was found to back extract the uranyl ion almost quantitatively (99.9 %) from the loaded organic phase but overall stripping from ionic liquid phase is comparatively poorer than that of xylene phase. The processing of Simulated High Level Waste (SHLW) of Pressurized Heavy Water Reactor (PHWR) or Research Reactor (RR) origin revealed that bis(2,4,4-trimethylpentyl phosphinic) acid can effectively be used for the preferential extraction of U with better selectivity for ionic liquid phase. But the ion exchange mechanism is one of the disadvantages for its plant scale application. (author)

  19. Mechanism of Supercooled Water Droplet Breakup near the Leading Edge of an Airfoil

    Science.gov (United States)

    Veras-Alba, Belen; Palacios, Jose; Vargas, Mario; Ruggeri, Charles; Bartkus, Tadas P.

    2017-01-01

    This work presents the results of an experimental study on supercooled droplet deformation and breakup near the leading edge of an airfoil. The results are compared to prior room temperature droplet deformation results to explore the effects of droplet supercooling. The experiments were conducted in the Adverse Environment Rotor Test Stand (AERTS) at The Pennsylvania State University. An airfoil model placed at the end of the rotor blades mounted onto the hub in the AERTS chamber was moved at speeds ranging between 50 and 80 m/sec. The temperature of the chamber was set at -20°C. A monotonic droplet generator was used to produce droplets that fell from above, perpendicular to the path of the airfoil. The supercooled state of the droplets was determined by measurement of the temperature of the drops at various locations below the droplet generator exit. A temperature prediction code was also used to estimate the temperature of the droplets based on vertical velocity and the distance traveled by droplets from the droplet generator to the airfoil stagnation line. High speed imaging was employed to observe the interaction between the droplets and the airfoil. The high speed imaging provided droplet deformation information as the droplet approached the airfoil near the stagnation line. A tracking software program was used to measure the horizontal and vertical displacement of the droplet against time. It was demonstrated that to compare the effects of water supercooling on droplet deformation, the ratio of the slip velocity and the initial droplet velocity must be equal. A case with equal slip velocity to initial velocity ratios was selected for room temperature and supercooled droplet conditions. The airfoil velocity was 60 m/s and the slip velocity for both sets of data was 40 m/s. In these cases, the deformation of the weakly supercooled and warm droplets did not present different trends. The similar behavior for both environmental conditions indicates that water

  20. Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin

    Science.gov (United States)

    2016-01-01

    This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4℃ for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4℃. Despite that SSF was conducted with the same method with SAF, application of artificial supercooling accelerated the phase transition (traverse from -0.6℃ to -5℃) from 3.07 h (SAF) to 2.23 h (SSF). The observation of a microstructure indicated that the SSF prevented tissue damage caused by ice crystallization and maintained the structural integrity. The estimated quality parameters reflected that SSF exhibited superior meat quality compared with slow freezing (SAF). SSF showed better water-holding capacity (lower thawing loss, cooking loss and expressible moisture) and tenderness than SAF, and these quality parameters of SSF were not significantly different with ultra-fast freezing treatment (EIF). Consequently, the results demonstrated that the generation of supercooling followed by conventional freezing potentially had the advantage of minimizing the quality deterioration caused by the slow freezing of meat. PMID:27857541

  1. Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin.

    Science.gov (United States)

    Kim, Yiseul; Hong, Geun-Pyo

    2016-10-31

    This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4℃ for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4℃. Despite that SSF was conducted with the same method with SAF, application of artificial supercooling accelerated the phase transition (traverse from -0.6℃ to -5℃) from 3.07 h (SAF) to 2.23 h (SSF). The observation of a microstructure indicated that the SSF prevented tissue damage caused by ice crystallization and maintained the structural integrity. The estimated quality parameters reflected that SSF exhibited superior meat quality compared with slow freezing (SAF). SSF showed better water-holding capacity (lower thawing loss, cooking loss and expressible moisture) and tenderness than SAF, and these quality parameters of SSF were not significantly different with ultra-fast freezing treatment (EIF). Consequently, the results demonstrated that the generation of supercooling followed by conventional freezing potentially had the advantage of minimizing the quality deterioration caused by the slow freezing of meat.

  2. Experimental evidence for stochastic switching of supercooled phases in NdNiO3 nanostructures

    Science.gov (United States)

    Kumar, Devendra; Rajeev, K. P.; Alonso, J. A.

    2018-03-01

    A first-order phase transition is a dynamic phenomenon. In a multi-domain system, the presence of multiple domains of coexisting phases averages out the dynamical effects, making it nearly impossible to predict the exact nature of phase transition dynamics. Here, we report the metal-insulator transition in samples of sub-micrometer size NdNiO3 where the effect of averaging is minimized by restricting the number of domains under study. We observe the presence of supercooled metallic phases with supercooling of 40 K or more. The transformation from the supercooled metallic to the insulating state is a stochastic process that happens at different temperatures and times in different experimental runs. The experimental results are understood without incorporating material specific properties, suggesting that the behavior is of universal nature. The size of the sample needed to observe individual switching of supercooled domains, the degree of supercooling, and the time-temperature window of switching are expected to depend on the parameters such as quenched disorder, strain, and magnetic field.

  3. On the molecular anisotropy of liquid crystalline and flexible polymer systems

    Science.gov (United States)

    van Horn, Brett L.

    The demand for products of ever increasing quality or for novel applications has required increasing attention to or manipulation of the anisotropy of manufactured parts. Oriented plastics are used everywhere from recording film to automotive body parts to monofilament fishing line. Liquid crystals are also used in a wide array of applications including their dominance in the flat panel display industry, color changing temperature sensors, and woven bullet resistant fabrics. Anisotropy can also be detrimental, for instance sometimes leading to poor fracture resistance or low yield stress along specific directions. Controlling and measuring anisotropy of materials has become increasingly important, but doing so is wrought with challenges. Measuring physical properties of isotropic liquids, such as water or most oils can be done in a straightforward fashion. Their viscosities and densities, for example, have unique values under a given set of conditions. With anisotropic fluids, like liquid crystals, the viscosity, for instance, will not only depend upon temperature, concentration, etc. but also upon the direction of observation, degree of anisotropy, source of anisotropy, and so forth. This added degree of complexity complicates our ability to define the state of the material at which the measurements are made and generally necessitates the use of more sophisticated measurement strategies or techniques. This work presents techniques and tools for investigating anisotropy in liquid crystalline and stretched polymeric systems. Included are the use of conoscopy for the determination of birefringence and orientation of nematic liquid crystals and stretched polymers, the shear response of flow aligning nematic liquid crystal monodomains, and the design of a novel linear rheometer that allows for in situ optical or scattering investigations.

  4. Molecular dynamics study on the effect of boundary heating rate on the phase change characteristics of thin film liquid

    Energy Technology Data Exchange (ETDEWEB)

    Hasan, Mohammad Nasim, E-mail: nasim@me.buet.ac.bd.com; Morshed, A. K. M. Monjur, E-mail: shavik@me.buet.ac.bd.com; Rabbi, Kazi Fazle, E-mail: rabbi35.me10@gmail.com; Haque, Mominul, E-mail: mominulmarup@gmail.com [Department of Mechanical Engineering, Bangladesh University of Engineering and Technology (BUET) Dhaka-1000 (Bangladesh)

    2016-07-12

    In this study, theoretical investigation of thin film liquid phase change phenomena under different boundary heating rates has been conducted with the help of molecular dynamics simulation. To do this, the case of argon boiling over a platinum surface has been considered. The study has been conducted to get a better understanding of the nano-scale physics of evaporation/boiling for a three phase system with particular emphasis on the effect of boundary heating rate. The simulation domain consisted of liquid and vapor argon atoms placed over a platinum wall. Initially the whole system was brought to an equilibrium state at 90 K with the help of equilibrium molecular dynamics and then the temperature of the bottom wall was increased to a higher temperature (250 K/130 K) over a finite heating period. Depending on the heating period, the boundary heating rate has been varied in the range of 1600×10{sup 9} K/s to 8×10{sup 9} K/s. The variations of argon region temperature, pressure, net evaporation number with respect to time under different boundary heating rates have been determined and discussed. The heat fluxes normal to platinum wall for different cases were also calculated and compared with theoretical upper limit of maximum possible heat transfer to elucidate the effect of boundary heating rate.

  5. SERS- and Electrochemically Active 3D Plasmonic Liquid Marbles for Molecular-Level Spectroelectrochemical Investigation of Microliter Reactions.

    Science.gov (United States)

    Koh, Charlynn Sher Lin; Lee, Hiang Kwee; Phan-Quang, Gia Chuong; Han, Xuemei; Lee, Mian Rong; Yang, Zhe; Ling, Xing Yi

    2017-07-17

    Liquid marbles are emergent microreactors owing to their isolated environment and the flexibility of materials used. Plasmonic liquid marbles (PLMs) are demonstrated as the smallest spectroelectrochemical microliter-scale reactor for concurrent spectro- and electrochemical analyses. The three-dimensional Ag shell of PLMs are exploited as a bifunctional surface-enhanced Raman scattering (SERS) platform and working electrode for redox process modulation. The combination of SERS and electrochemistry (EC) capabilities enables in situ molecular read-out of transient electrochemical species, and elucidate the potential-dependent and multi-step reaction dynamics. The 3D configuration of our PLM-based EC-SERS system exhibits 2-fold and 10-fold superior electrochemical and SERS performance than conventional 2D platforms. The rich molecular-level electrochemical insights and excellent EC-SERS capabilities offered by our 3D spectroelectrochemical system are pertinent in charge transfer processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Revisiting imidazolium based ionic liquids: Effect of the conformation bias of the [NTf2] anion studied by molecular dynamics simulations

    Science.gov (United States)

    Neumann, Jan; Golub, Benjamin; Odebrecht, Lisa-Marie; Ludwig, Ralf; Paschek, Dietmar

    2018-05-01

    We study ionic liquids composed of 1-alkyl-3-methylimidazolium cations and bis(trifluoromethyl-sulfonyl)imide anions ([CnMIm][NTf2]) with varying chain-length n = 2, 4, 6, 8 by using molecular dynamics simulations. We show that a reparametrization of the dihedral potentials as well as charges of the [NTf2] anion leads to an improvement of the force field model introduced by Köddermann, Paschek, and Ludwig [ChemPhysChem 8, 2464 (2007)] (KPL-force field). A crucial advantage of the new parameter set is that the minimum energy conformations of the anion (trans and gauche), as deduced from ab initio calculations and Raman experiments, are now both well represented by our model. In addition, the results for [CnMIm][NTf2] show that this modification leads to an even better agreement between experiment and molecular dynamics simulation as demonstrated for densities, diffusion coefficients, vaporization enthalpies, reorientational correlation times, and viscosities. Even though we focused on a better representation of the anion conformation, also the alkyl chain-length dependence of the cation behaves closer to the experiment. We strongly encourage to use the new NGOLP (Neumann, Golub, Odebrecht, Ludwig, Paschek) force field for the [NTf2] anion instead of the earlier KPL parameter set for computer simulations aiming to describe the thermodynamics, dynamics, and also structure of imidazolium-based ionic liquids.

  7. Molecular structure of the discotic liquid crystalline phase of hexa-peri-hexabenzocoronene/oligothiophene hybrid and their charge transport properties

    International Nuclear Information System (INIS)

    Bag, Saientan; Maingi, Vishal; Maiti, Prabal K.; Yelk, Joe; Glaser, Matthew A.; Clark, Noel A.; Walba, David M.

    2015-01-01

    Using atomistic molecular dynamics simulation, we study the discotic columnar liquid crystalline (LC) phases formed by a new organic compound having hexa-peri-Hexabenzocoronene (HBC) core with six pendant oligothiophene units recently synthesized by Nan Hu et al. [Adv. Mater. 26, 2066 (2014)]. This HBC core based LC phase was shown to have electric field responsive behavior and has important applications in organic electronics. Our simulation results confirm the hexagonal arrangement of columnar LC phase with a lattice spacing consistent with that obtained from small angle X-ray diffraction data. We have also calculated various positional and orientational correlation functions to characterize the ordering of the molecules in the columnar arrangement. The molecules in a column are arranged with an average twist of 25° having an average inter-molecular separation of ∼5 Å. Interestingly, we find an overall tilt angle of 43° between the columnar axis and HBC core. We also simulate the charge transport through this columnar phase and report the numerical value of charge carrier mobility for this liquid crystal phase. The charge carrier mobility is strongly influenced by the twist angle and average spacing of the molecules in the column

  8. The atomic-scale nucleation mechanism of NiTi metallic glasses upon isothermal annealing studied via molecular dynamics simulations.

    Science.gov (United States)

    Li, Yang; Li, JiaHao; Liu, BaiXin

    2015-10-28

    Nucleation is one of the most essential transformation paths in phase transition and exerts a significant influence on the crystallization process. Molecular dynamics simulations were performed to investigate the atomic-scale nucleation mechanisms of NiTi metallic glasses upon devitrification at various temperatures (700 K, 750 K, 800 K, and 850 K). Our simulations reveal that at 700 K and 750 K, nucleation is polynuclear with high nucleation density, while at 800 K it is mononuclear. The underlying nucleation mechanisms have been clarified, manifesting that nucleation can be induced either by the initial ordered clusters (IOCs) or by the other precursors of nuclei evolved directly from the supercooled liquid. IOCs and other precursors stem from the thermal fluctuations of bond orientational order in supercooled liquids during the quenching process and during the annealing process, respectively. The simulation results not only elucidate the underlying nucleation mechanisms varied with temperature, but also unveil the origin of nucleation. These discoveries offer new insights into the devitrification mechanism of metallic glasses.

  9. Induction of liquid crystallinity of by self-assembled molecular boxes

    NARCIS (Netherlands)

    Piermattei, A.; Giesbers, Marcel; Marcelis, Antonius T.M.; Mendes, Eduardo; Picken, Stephen J.; Crego Calama, Mercedes; Reinhoudt, David

    2006-01-01

    Jewel-box: In a hierarchical process, three molecules of a calix[4]arene (blue) and six of barbituric or cyanuric acid (green) assemble into double-rosette boxes, which assemble into columns, which in turn assemble into columnar liquid-crystalline phases (see picture). The resulting mesophases have

  10. H-1 NMR relaxometric study of molecular dynamics in a "de Vries" liquid crystal

    Czech Academy of Sciences Publication Activity Database

    Gradišek, A.; Domenici, V.; Apih, T.; Novotná, Vladimíra; Sebastiao, P.J.

    2016-01-01

    Roč. 120, č. 20 (2016), s. 4706-4714 ISSN 1520-6106 Grant - others:AVČR(CZ) M100101204 Institutional support: RVO:68378271 Keywords : liquid crystals Subject RIV: JJ - Other Materials Impact factor: 3.177, year: 2016

  11. Visualizing Molecular Chirality in the Organic Chemistry Laboratory Using Cholesteric Liquid Crystals

    Science.gov (United States)

    Popova, Maia; Bretz, Stacey Lowery; Hartley, C. Scott

    2016-01-01

    Although stereochemistry is an important topic in second-year undergraduate organic chemistry, there are limited options for laboratory activities that allow direct visualization of macroscopic chiral phenomena. A novel, guided-inquiry experiment was developed that allows students to explore chirality in the context of cholesteric liquid crystals.…

  12. Pair Potential That Reproduces the Shape of Isochrones in Molecular Liquids

    DEFF Research Database (Denmark)

    Veldhorst, Arno; Schrøder, Thomas; Dyre, Jeppe C.

    2016-01-01

    -dependent function of density, h(ρ), which for real liquids is well approximated by a power law, ργ. However, in simulations, a power law is not adequate when density changes are large; typical models, such as Lennard-Jones liquids, show that γ(ρ) ≡ d ln h(ρ)/d ln ρ is a decreasing function of density. This article...... presents results from computer simulations using a new pair potential that diverges at a nonzero distance and can be tuned to give a more realistic shape of γ(ρ). Our results indicate that the finite size of molecules is an important factor to take into account when modeling liquids over a large density......Many liquids have curves (isomorphs) in their phase diagrams along which structure, dynamics, and some thermodynamic quantities are invariant in reduced units. A substantial part of their phase diagrams is thus effectively one dimensional. The shapes of these isomorphs are described by a material...

  13. Application of Molecular Simulations: Insight into Liquid Bridging and Jetting Phenomena.

    Czech Academy of Sciences Publication Activity Database

    Nezbeda, Ivo; Jirsák, J.; Moučka, F.; Smith, W.R.

    2015-01-01

    Roč. 18, č. 1 (2015), s. 13602 ISSN 1607-324X Institutional support: RVO:67985858 Keywords : aqueous solution surfaces * floating liquid bridge * aqueous solution surfaces Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.621, year: 2015

  14. Branched and Cyclic Alkyl Groups in Imidazolium - Based Ionic Liquids: Molecular Organization and Physico - chemical Properties

    Czech Academy of Sciences Publication Activity Database

    Andresová, Adéla; Storch, Jan; Traikia, M.; Wagner, Zdeněk; Bendová, Magdalena; Husson, P.

    2014-01-01

    Roč. 371, JUN 15 (2014), s. 41-49 ISSN 0378-3812 R&D Projects: GA MŠk(CZ) LG12032 Institutional support: RVO:67985858 Keywords : ionic liquids * sythesis * density Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.200, year: 2014

  15. Molecular scale structure and dynamics at an ionic liquid/electrode interface

    DEFF Research Database (Denmark)

    Reichert, Peter; Kjær, Kasper Skov; Brandt van Driel, Tim

    2018-01-01

    After a century of research, the potential-dependent ion distribution at electrode/electrolyte interfaces is still under debate. In particular for solvent-free electrolytes such as room-temperature ionic liquids, classical theories for the electrical double layer are not applicable. Using a combi...

  16. Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

    Science.gov (United States)

    Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

    2018-05-01

    Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

  17. Vibrational circular dichroism from ab initio molecular dynamics and nuclear velocity perturbation theory in the liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Scherrer, Arne [Martin-Luther-Universität Halle-Wittenberg, Institut für Chemie, von-Danckelmann-Platz 4, 06120 Halle (Germany); Département de Chimie, École Normale supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, PASTEUR, 24 rue Lhomond, 75005 Paris (France); Sorbonne Universités, UPMC Univ Paris 06, ENS, CNRS, PASTEUR, 75005 Paris (France); Vuilleumier, Rodolphe, E-mail: rodolphe.vuilleumier@ens.fr [Département de Chimie, École Normale supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, PASTEUR, 24 rue Lhomond, 75005 Paris (France); Sorbonne Universités, UPMC Univ Paris 06, ENS, CNRS, PASTEUR, 75005 Paris (France); Sebastiani, Daniel, E-mail: daniel.sebastiani@chemie.uni-halle.de [Martin-Luther-Universität Halle-Wittenberg, Institut für Chemie, von-Danckelmann-Platz 4, 06120 Halle (Germany)

    2016-08-28

    We report the first fully ab initio calculation of dynamical vibrational circular dichroism spectra in the liquid phase using nuclear velocity perturbation theory (NVPT) derived electronic currents. Our approach is rigorous and general and thus capable of treating weak interactions of chiral molecules as, e.g., chirality transfer from a chiral molecule to an achiral solvent. We use an implementation of the NVPT that is projected along the dynamics to obtain the current and magnetic dipole moments required for accurate intensities. The gauge problem in the liquid phase is resolved in a twofold approach. The electronic expectation values are evaluated in a distributed origin gauge, employing maximally localized Wannier orbitals. In a second step, the gauge invariant spectrum is obtained in terms of a scaled molecular moments, which allows to systematically include solvent effects while keeping a significant signal-to-noise ratio. We give a thorough analysis and discussion of this choice of gauge for the liquid phase. At low temperatures, we recover the established double harmonic approximation. The methodology is applied to chiral molecules ((S)-d{sub 2}-oxirane and (R)-propylene-oxide) in the gas phase and in solution. We find an excellent agreement with the theoretical and experimental references, including the emergence of signals due to chirality transfer from the solute to the (achiral) solvent.

  18. Evolution of short range order in Ar: Liquid to glass and solid transitions-A computational study

    Science.gov (United States)

    Shor, Stanislav; Yahel, Eyal; Makov, Guy

    2018-04-01

    The evolution of the short range order (SRO) as a function of temperature in a Lennard-Jones model liquid with Ar parameters was determined and juxtaposed with thermodynamic and kinetic properties obtained as the liquid was cooled (heated) and transformed between crystalline solid or glassy states and an undercooled liquid. The Lennard-Jones system was studied by non-equilibrium molecular dynamics simulations of large supercells (approximately 20000 atoms) rapidly cooled or heated at selected quenching rates and at constant pressure. The liquid to solid transition was identified by discontinuities in the atomic volume and molar enthalpy; the glass transition temperature range was identified from the temperature dependence of the self-diffusion. The SRO was studied within the quasi-crystalline model (QCM) framework and compared with the Steinhardt bond order parameters. Within the QCM it was found that the SRO evolves from a bcc-like order in the liquid through a bct-like short range order (c/a=1.2) in the supercooled liquid which persists into the glass and finally to a fcc-like ordering in the crystalline solid. The variation of the SRO that results from the QCM compares well with that obtained with Steinhardt's bond order parameters. The hypothesis of icosahedral order in liquids and glasses is not supported by our results.

  19. Ab initio molecular dynamics study of temperature and pressure-dependent infrared dielectric functions of liquid methanol

    Directory of Open Access Journals (Sweden)

    C. C. Wang

    2017-03-01

    Full Text Available The temperature and pressure-dependent dielectric functions of liquids are of great importance to the thermal radiation transfer and the diagnosis and control of fuel combustion. In this work, we apply the state-of-the-art ab initio molecular dynamics (AIMD method to calculate the infrared dielectric functions of liquid methanol at 183–573 K and 0.1–160 MPa in the spectral range 10−4000 cm−1, and study the temperature and pressure effects on the dielectric functions. The AIMD approach is validated by the Infrared Variable Angle Spectroscopic Ellipsometry (IR-VASE experimental measurements at 298 K and 0.1 MPa, and the proposed IR-VASE method is verified by comparison with paper data of distilled water. The results of the AIMD approach agrees well with the experimental values of IR-VASE. The experimental and theoretical analyses indicate that the temperature and pressure exert a noticeable influence on the infrared dielectric functions of liquid methanol. As temperature increases, the average molecular dipole moment decreases. The amplitudes of dominant absorption peaks reduce to almost one half as temperature increases from 183 to 333 K at 0.1 MPa and from 273 to 573 K at 160 MPa. The absorption peaks below 1500 cm–1 show a redshift, while those centered around 3200 cm–1 show a blueshift. Moreover, larger average dipole moments are observed as pressure increases. The amplitudes of dominant absorption peaks increase to almost two times as pressure increases from 1 to 160 MPa at 373 K.

  20. The Putative Liquid-Liquid Transition is a Liquid-Solid Transition in Atomistic Models of Water

    Science.gov (United States)

    Chandler, David; Limmer, David

    2013-03-01

    Our detailed and controlled studies of free energy surfaces for models of water find no evidence for reversible polyamorphism, and a general theoretical analysis of the phase behavior of cold water in nano pores shows that measured behaviors of these systems reflect surface modulation and dynamics of ice, not a liquid-liquid critical point. A few workers reach different conclusions, reporting evidence of a liquid-liquid critical point in computer simulations of supercooled water. In some cases, it appears that these contrary results are based upon simulation algorithms that are inconsistent with principles of statistical mechanics, such as using barostats that do not reproduce the correct distribution of volume fluctuations. In other cases, the results appear to be associated with difficulty equilibrating the supercooled material and mistaking metastability for coarsening of the ordered ice phase. In this case, sufficient information is available for us to reproduce the contrary results and to establish that they are artifacts of finite time sampling. This finding leads us to the conclusion that two distinct, reversible liquid phases do not exist in models of supercooled water.

  1. Development of seasonal heat storage based on stable supercooling of a sodium acetate water mixture

    DEFF Research Database (Denmark)

    Furbo, Simon; Fan, Jianhua; Andersen, Elsa

    2012-01-01

    A number of heat storage modules for seasonal heat storages based on stable supercooling of a sodium acetate water mixture have been tested by means of experiments in a heat storage test facility. The modules had different volumes and designs. Further, different methods were used to transfer heat...... to and from the sodium acetate water mixture in the modules. By means of the experiments: • The heat exchange capacity rates to and from the sodium acetate water mixture in the heat storage modules were determined for different volume flow rates. • The heat content of the heat storage modules were determined....... • The reliability of the supercooling was elucidated for the heat storage modules for different operation conditions. • The reliability of a cooling method used to start solidification of the supercooled sodium acetate water mixture was elucidated. The method is making use of boiling CO2 in a small tank in good...

  2. Limited Impact of Subglacial Supercooling Freeze-on for Greenland Ice Sheet Stratigraphy

    Science.gov (United States)

    Dow, Christine F.; Karlsson, Nanna B.; Werder, Mauro A.

    2018-02-01

    Large units of disrupted radiostratigraphy (UDR) are visible in many radio-echo sounding data sets from the Greenland Ice Sheet. This study investigates whether supercooling freeze-on rates at the bed can cause the observed UDR. We use a subglacial hydrology model to calculate both freezing and melting rates at the base of the ice sheet in a distributed sheet and within basal channels. We find that while supercooling freeze-on is a phenomenon that occurs in many areas of the ice sheet, there is no discernible correlation with the occurrence of UDR. The supercooling freeze-on rates are so low that it would require tens of thousands of years with minimal downstream ice motion to form the hundreds of meters of disrupted radiostratigraphy. Overall, the melt rates at the base of the ice sheet greatly overwhelm the freeze-on rates, which has implications for mass balance calculations of Greenland ice.

  3. Molecular tilt near nanoparticles in the smectic A phase of de Vries liquid-crystalline compound

    Czech Academy of Sciences Publication Activity Database

    Lejček, Lubor; Novotná, Vladimíra; Glogarová, Milada

    2014-01-01

    Roč. 89, č. 1 (2014), "012505-1"-"012505-6" ISSN 1539-3755 R&D Projects: GA ČR(CZ) GAP204/11/0723 Institutional support: RVO:68378271 Keywords : liquid crystals * smectic phases * nanoparticles * deVries behaviour Subject RIV: JJ - Other Materials Impact factor: 2.288, year: 2014 http://pre. aps .org/abstract/PRE/v89/i1/e012505

  4. Enzyme kinetics in acoustically levitated droplets of supercooled water: a novel approach to cryoenzymology.

    Science.gov (United States)

    Weis, David D; Nardozzi, Jonathan D

    2005-04-15

    The rate of the alkaline phosphatase-catalyzed hydrolysis of 4-methylumbelliferone phosphate was measured in acoustically levitated droplets of aqueous tris (50 mM) at pH 8.5 at 22 +/- 2 degrees C and in supercooled solution at -6 +/- 2 degrees C. At 22 degrees C, the rate of product formation was in excellent agreement with the rate observed in bulk solution in a cuvette, indicating that the acoustic levitation process does not alter the enzyme activity. The rate of the reaction decreased 6-fold in supercooled solution at -6 +/- 2 degrees C. The acoustic levitator apparatus is described in detail.

  5. Molecularly Imprinted Polymers (MIP for Selective Solid Phase Extraction of Celecoxib in Urine Samples Followed by High Performance Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Saeedeh Ansari

    2017-09-01

    Full Text Available In this study, for the analysis of human urine samples, a novel method explained for the determination of celecoxib, a nonsteroidal anti-inflammatory drug (NSAID, using molecularly imprinted solid-phase extraction (MISPE coupled with high-performance liquid chromatography (HPLC. The synthesis of the MIP was performed by precipitation polymerization in methacrylic acid (MAA, ethylene glycol dimethacrylate (EGDMA, chloroform, 2,2′-azobisisobutyronitrile (AIBN and celecoxib as the functional monomer, cross-linker monomer, solvent, initiator and target drug, respectively. The celecoxib imprinted polymer was utilized as a specific sorbent for the solid phase extraction (SPE of celecoxib from samples. The molecularly imprinted polymer (MIP performance was compared with the synthesized non-molecularly imprinted polymer (NIP. Scanning electron microscopy (SEM, FT-IR spectroscopy, UV-VIS spectrophotometry and thermogravimetric analysis (TGA/DTG were used for characterizing the synthesized polymers. Moreover, the MISPE procedure parameters such as pH, eluent solvent flow rate, eluent volume and sorbent mass that probably influence the extraction process have been optimized to achieve the highest celecoxib extraction efficiency. The relative standard deviation (RSD %, recovery percent, limit of detection (LOD and limit of quantification (LOQ of this proposed method were 1.12%, 96%, 8 µg L-1 and 26.7 µg L-1, respectively. The proposed MISPE-HPLC-UV method can be used for the separation and enrichment of trace amounts of celecoxib in human urine and biological samples.

  6. Stability optimisation of molecular electronic devices based on  nanoelectrode–nanoparticle bridge platform in air and different storage liquids

    International Nuclear Information System (INIS)

    Jafri, S. H. M.; Blom, T.; Wallner, A.; Ottosson, H.; Leifer, K.

    2014-01-01

    The long-term stability of metal nanoparticle–molecule junctions in molecular electronic devices based on nanoelectrodes (NEL) is a major challenge in the effort to bring related molecular electronic devices to application. To optimize the reproducibility of molecular electronic nanodevices, the time-dependent modification of such junctions as exposed to different media needs to be known. Here, we have studied (1) the stability of Au-NEL and (2) the electrical stability of molecule–Au nanoparticle (AuNP) junctions themselves with the molecule being  1,8-octanedithiol (ODT). Both the NELs only and the junctions were exposed to air and liquids such as deionized water, tetrahydrofuran, toluene and tetramethylethylenediamine (TMEDA) over a period of 1 month. The nanogaps remained stable in width when stored in either deionized water or toluene, whereas the current through 1,8-octanedithiol–NP junctions remained most stable when stored in TMEDA as compared to other solvents. Although it is difficult to follow the chemical processes in such devices in the 10-nm range with analytical methods, the behavior can be interpreted from known interactions of solvent molecules with electrodes and ODT

  7. A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: Multi-center molecular Ornstein-Zernike self-consistent field approach

    Science.gov (United States)

    Kido, Kentaro; Kasahara, Kento; Yokogawa, Daisuke; Sato, Hirofumi

    2015-07-01

    In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein-Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple SN2 reaction (Cl- + CH3Cl → ClCH3 + Cl-) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF.

  8. A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: Multi-center molecular Ornstein–Zernike self-consistent field approach

    International Nuclear Information System (INIS)

    Kido, Kentaro; Kasahara, Kento; Yokogawa, Daisuke; Sato, Hirofumi

    2015-01-01

    In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein–Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple S N 2 reaction (Cl − + CH 3 Cl → ClCH 3 + Cl − ) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF

  9. A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: multi-center molecular Ornstein-Zernike self-consistent field approach.

    Science.gov (United States)

    Kido, Kentaro; Kasahara, Kento; Yokogawa, Daisuke; Sato, Hirofumi

    2015-07-07

    In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein-Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple SN2 reaction (Cl(-) + CH3Cl → ClCH3 + Cl(-)) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF.

  10. New Mexico cloud super cooled liquid water survey final report 2009.

    Energy Technology Data Exchange (ETDEWEB)

    Beavis, Nick; Roskovensky, John K.; Ivey, Mark D.

    2010-02-01

    Los Alamos and Sandia National Laboratories are partners in an effort to survey the super-cooled liquid water in clouds over the state of New Mexico in a project sponsored by the New Mexico Small Business Assistance Program. This report summarizes the scientific work performed at Sandia National Laboratories during the 2009. In this second year of the project a practical methodology for estimating cloud super-cooled liquid water was created. This was accomplished through the analysis of certain MODIS sensor satellite derived cloud products and vetted parameterizations techniques. A software code was developed to analyze multiple cases automatically. The eighty-one storm events identified in the previous year effort from 2006-2007 were again the focus. Six derived MODIS products were obtained first through careful MODIS image evaluation. Both cloud and clear-sky properties from this dataset were determined over New Mexico. Sensitivity studies were performed that identified the parameters which most influenced the estimation of cloud super-cooled liquid water. Limited validation was undertaken to ensure the soundness of the cloud super-cooled estimates. Finally, a path forward was formulized to insure the successful completion of the initial scientific goals which include analyzing different of annual datasets, validation of the developed algorithm, and the creation of a user-friendly and interactive tool for estimating cloud super-cooled liquid water.

  11. Molecular species composition of plant cardiolipin determined by liquid chromatography mass spectrometry

    Science.gov (United States)

    Zhou, Yonghong; Peisker, Helga

    2016-01-01

    Cardiolipin (CL), an anionic phospholipid of the inner mitochondrial membrane, provides essential functions for stabilizing respiratory complexes and is involved in mitochondrial morphogenesis and programmed cell death in animals. The role of CL and its metabolism in plants are less well understood. The measurement of CL in plants, including its molecular species composition, is hampered by the fact that CL is of extremely low abundance, and that plants contain large amounts of interfering compounds including galactolipids, neutral lipids, and pigments. We used solid phase extraction by anion exchange chromatography to purify CL from crude plant lipid extracts. LC/MS was used to determine the content and molecular species composition of CL. Thus, up to 23 different molecular species of CL were detected in different plant species, including Arabidopsis, mung bean, spinach, barley, and tobacco. Similar to animals, plant CL is dominated by highly unsaturated species, mostly containing linoleic and linolenic acid. During phosphate deprivation or exposure to an extended dark period, the amount of CL decreased in Arabidopsis, accompanied with an increased degree in unsaturation. The mechanism of CL remodeling during stress, and the function of highly unsaturated CL molecular species, remains to be defined. PMID:27179363

  12. Detailed intermolecular structure of molecular liquids containing slightly distorted tetrahedral molecules with C(3v) symmetry: chloroform, bromoform, and methyl-iodide.

    Science.gov (United States)

    Pothoczki, Szilvia; Temleitner, László; Pusztai, László

    2011-01-28

    Analyses of the intermolecular structure of molecular liquids containing slightly distorted tetrahedral molecules of the CXY(3)-type are described. The process is composed of the determination of several different distance-dependent orientational correlation functions, including ones that are introduced here. As a result, a complete structure classification could be provided for CXY(3) molecular liquids, namely for liquid chloroform, bromoform, and methyl-iodide. In the present work, the calculations have been conducted on particle configurations resulting from reverse Monte Carlo computer modeling: these particle arrangements have the advantage that they are fully consistent with structure factors from neutron and x-ray diffraction measurements. It has been established that as the separation between neighboring molecules increases, the dominant mutual orientations change from face-to-face to edge-to-edge, via the edge-to-face arrangements. Depending on the actual liquid, these geometrical elements (edges and faces of the distorted tetrahedra) were found to contain different atoms. From the set of liquids studied here, the structure of methyl-iodide was found to be easiest to describe on the basis of pure steric effects (molecular shape, size, and density) and the structure of liquid chloroform seems to be the furthest away from the corresponding "flexible fused hard spheres" like reference system.

  13. Hydrogen bonding discotic liquid crystals: Synthesis, self-assembly, and molecular recognition

    Science.gov (United States)

    Bushey, Mark Lawrence

    The triamides shown below form discotic liquid crystalline phases with intermolecular hydrogen bonding stabilizing the columnar structure, A and B. The mesomorphic orientations of the columns are dependent on the amide side chain. Three mesophasic orientations are described: columns aligned perpendicular to the surface, columns aligned parallel to the surface in a radial pattern, and columns aligned parallel to the surface in a parallel or aligned pattern. The aggregation of the tridodecyloxy-triamides show N-H shifting in the IR at elevated temperatures, an indication that hydrogen bonding is important in the association of liquid crystalline mesophases. Powder X-ray diffraction studies indicate packing of the columns into a hexagonal lattice.* Studies on triamides with chiral side chains result in molecules stacking into columns displaying a helical pitch. In concentrated solutions of dodecane, molecules with chiral side chains display behavior consistent with chiral nematic liquid crystals; a super helical packing of the chiral columns. These superhelical packed systems show temperature dependent selective reflection of visible light and fingerprint textures. Atomic force microscopy (AFM) confirms in sub-monolayer films, that molecules preferring an edge-on orientation form long columns on highly ordered pyrolytic graphite (HOPG), those that prefer a face-on orientation form large amorphous domains. Electrostatic force microscopy (EFM) images of the domains of molecules in the edge-on orientation provides no discernible polarity, imaging of the domains of molecules in the face-on orientation indicates a negative polar orientation. Scanning probe measurements (SPM) of the tridodecynyl-triamide have shown similar edge-on orientations of other tridodecyloxy-triamides. Powder X-ray diffraction of these liquid crystalline phases shows a hexagonal packing of the columnar assembly. Electro-optic switching studies indicate a piezoelectric switching mechanism, possibly

  14. Characterization of surfactant liquid crystal phases suitable for molecular alignment and measurement of dipolar couplings

    International Nuclear Information System (INIS)

    Barrientos, Laura G.; Dolan, Caroline; Gronenborn, Angela M.

    2000-01-01

    Media employed for imparting partial alignment onto solute molecules have recently attracted considerable attention, since they permit the measurement of NMR parameters for solute biomolecules commonly associated with solid state NMR. Here we characterize a medium which is based on a quasi-ternary surfactant system comprising cetylpyridinium bromide/hexanol/sodium bromide. We demonstrate that dilute solutions of this system can exist in liquid crystalline phases which orient in the magnetic field and allow the measurement of residual dipolar couplings under a variety of conditions. The present system is extremely versatile and robust, tolerating different buffer conditions, temperature ranges and concentrations

  15. Antiferroelectric phase in liquid crystalline compounds with azo group in their molecular core

    Czech Academy of Sciences Publication Activity Database

    Kašpar, Miroslav; Novotná, Vladimíra; Hamplová, Věra; Podoliak, Natalia; Nonnenmacher, D.; Giesselmann, F.; Glogarová, Milada

    2011-01-01

    Roč. 38, č. 3 (2011), s. 309-315 ISSN 0267-8292 R&D Projects: GA AV ČR IAA100100911; GA AV ČR(CZ) GA202/09/0047 Grant - others:German Czech bilateral program(DE) D4-CZ5/2010-2011; GA UK(CZ) SVV-2011-263303 Institutional research plan: CEZ:AV0Z10100520 Keywords : liquid crystals * antiferroelectricity * azo linkage group * photosensitivity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.858, year: 2011

  16. Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Johansen, P.M.

    1997-01-01

    . The theory provides an explanation for the high long-term stability of the photoinduced anisotropy as well as a theoretical prediction of the temporal behavior of photoinduced birefringence. The theoretical results agree favorably with measurements in the entire range of writing intensities used......A novel mean-field theory of photoinduced reorientation and optical anisotropy in liquid crystalline side-chain polymers is presented and compared with experiments, The reorientation mechanism is based on photoinduced trans cis isomerization and a multidomain model of the material is introduced...

  17. Influence of alkyl chain length and temperature on thermophysical properties of ammonium-based ionic liquids with molecular solvent.

    Science.gov (United States)

    Kavitha, T; Attri, Pankaj; Venkatesu, Pannuru; Devi, R S Rama; Hofman, T

    2012-04-19

    Mixing of ionic liquids (ILs) with molecular solvent can expand the range of structural properties and the scope of molecular interactions between the molecules of the solvents. Exploiting of these phenomena essentially require a basic fundamental understanding of mixing behavior of ILs with molecular solvents. In this context, a series of protic ILs possessing tetra-alkyl ammonium cation [R(4)N](+) with commonly used anion hydroxide [OH](-) were synthesized and characterized by temperature dependent thermophysical properties. The ILs [R(4)N](+)[OH](-) are varying only in the length of alkyl chain (R is methyl, ethyl, propyl, or butyl) of tetra-alkyl ammonium on the cationic part. The ILs used for the present study included tetramethyl ammonium hydroxide [(CH(3))(4)N](+)[OH](-) (TMAH), tetraethyl ammonium hydroxide [(C(2)H(5))(4)N](+)[OH](-) (TEAH), tetrapropyl ammonium hydroxide [(C(3)H(7))(4)N](+)[OH](-) (TPAH) and tetrabutyl ammonium hydroxide [(C(4)H(9))(4)N](+)[OH](-) (TBAH). The alkyl chain length effect has been analyzed by precise measurements such as densities (ρ), ultrasonic sound velocity (u), and viscosity (η) of these ILs with polar solvent, N-methyl-2-pyrrolidone (NMP), over the full composition range as a function of temperature. The excess molar volume (V(E)), the deviation in isentropic compressibility (Δκ(s)) and deviation in viscosity (Δη) were predicted using these properties as a function of the concentration of ILs. Redlich-Kister polynomial was used to correlate the results. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and NMP molecules. Later, the hydrogen bonding features between ILs and NMP were also analyzed using a molecular modeling program with the help of HyperChem 7.

  18. Effects of constituent ions of a phosphonium-based ionic liquid on molecular organization of H2O as probed by 1-propanol

    DEFF Research Database (Denmark)

    Morita, Takeshi; Miki, Kumiko; Ayako, Nitta

    2015-01-01

    on the basis of 1-propanol probing methodology devised by Koga et al. The resulting characterization of the hydrophobicity/hydrophilicity is displayed on a two-dimensional map together with previous results, for a total of four cations and nine anions of typical ionic liquid (IL) constituents. The results......Aqueous solutions of tetrabutylphosphonium trifluoroacetate, [P4444]CF3COO, exhibit a liquid-liquid phase transition with a lower critical solution temperature. Herein, we characterized the constituent ions, [P4444](+) and CF3COO(-), in terms of their effects on the molecular organization of H2O...

  19. Rock-salt structure lithium deuteride formation in liquid lithium with high-concentrations of deuterium: a first-principles molecular dynamics study

    Science.gov (United States)

    Chen, Mohan; Abrams, T.; Jaworski, M. A.; Carter, Emily A.

    2016-01-01

    Because of lithium’s possible use as a first wall material in a fusion reactor, a fundamental understanding of the interactions between liquid lithium (Li) and deuterium (D) is important. We predict structural and dynamical properties of liquid Li samples with high concentrations of D, as derived from first-principles molecular dynamics simulations. Liquid Li samples with four concentrations of inserted D atoms (LiDβ , β =0.25 , 0.50, 0.75, and 1.00) are studied at temperatures ranging from 470 to 1143 K. Densities, diffusivities, pair distribution functions, bond angle distribution functions, geometries, and charge transfer between Li and D atoms are calculated and analyzed. The analysis suggests liquid-solid phase transitions can occur at some concentrations and temperatures, forming rock-salt LiD within liquid Li. We also observe formation of some D2 molecules at high D concentrations.

  20. Transport coefficients of liquid CF4 and SF6 computed by molecular dynamics using polycenter Lennard-Jones potentials

    Science.gov (United States)

    Hoheisel, C.

    1989-01-01

    For several liquid states of CF4 and SF4, the shear and the bulk viscosity as well as the thermal conductivity were determined by equilibrium molecular dynamics (MD) calculations. Lennard-Jones four- and six-center pair potentials were applied, and the method of constraints was chosen for the MD. The computed Green-Kubo integrands show a steep time decay, and no particular longtime behavior occurs. The molecule number dependence of the results is found to be small, and 3×105 integration steps allow an accuracy of about 10% for the shear viscosity and the thermal conductivity coefficient. Comparison with experimental data shows a fair agreement for CF4, while for SF6 the transport coefficients fall below the experimental ones by about 30%.

  1. Transport coefficients of liquid CF4 and SF6 computed by molecular dynamics using polycenter Lennard-Jones potentials

    International Nuclear Information System (INIS)

    Hoheisel, C.

    1989-01-01

    For several liquid states of CF 4 and SF 6 , the shear and the bulk viscosity as well as the thermal conductivity were determined by equilibrium molecular dynamics (MD) calculations. Lennard-Jones four- and six-center pair potentials were applied, and the method of constraints were chosen for the MD. The computed Green-Kubo integrands show a steep time decay, and no particular longtime behavior occurs. The molecule number dependence of the results is found to be small, and 3 x 10 5 integration steps allow an accuracy of about 10% for the shear viscosity and the thermal conductivity coefficient. Comparison with experimental data shows a fair agreement for CF 4 , while for SF 6 the transport coefficients fall below the experimental ones by about 30%

  2. Molecular dynamics simulation of liquid structure for undercooled Zr-Nb alloys assisted with electrostatic levitation experiments

    Science.gov (United States)

    Yang, S. J.; Hu, L.; Wang, L.; Wei, B.

    2018-06-01

    The liquid structures of undercooled Zr90Nb10, Zr70Nb30 and Zr50Nb50 alloys were studied by molecular dynamics simulation combined with electrostatic levitation experiments. The densities of three alloys were measured by electrostatic levitation to modify the Zr-Nb potential functions by adjusting parameters in potential functions. In simulation, the atomic packing in Zr-Nb alloys was more ordered at lower temperatures. The Voronoi tessellation analyses indicated Nb-centered clusters were easier to form than Zr-centered clusters although the Nb content was less than 50%. The partial pair distribution functions showed that the interactions among Zr atoms are quite different to that among Nb atoms.

  3. Molecularly imprinted membrane extraction combined with high-performance liquid chromatography for selective analysis of cloxacillin from shrimp samples.

    Science.gov (United States)

    Du, Wei; Sun, Min; Guo, Pengqi; Chang, Chun; Fu, Qiang

    2018-09-01

    Nowadays, the abuse of antibiotics in aquaculture has generated considerable problems for food safety. Therefore, it is imperative to develop a simple and selective method for monitoring illegal use of antibiotics in aquatic products. In this study, a method combined molecularly imprinted membranes (MIMs) extraction and liquid chromatography was developed for the selective analysis of cloxacillin from shrimp samples. The MIMs was synthesized by UV photopolymerization, and characterized by scanning electron microscope, Fourier transform infrared spectra, thermo-gravimetric analysis and swelling test. The results showed that the MIMs exhibited excellent permselectivity, high adsorption capacity and fast adsorption rate for cloxacillin. Finally, the method was utilized to determine cloxacillin from shrimp samples, with good accuracies and acceptable relative standard deviation values for precision. The proposed method was a promising alternative for selective analysis of cloxacillin in shrimp samples, due to the easy-operation and excellent selectivity. Copyright © 2018. Published by Elsevier Ltd.

  4. Path integral centroid molecular dynamics simulations of semiinfinite slab and bulk liquid of para-hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kinugawa, Kenichi [Nara Women`s Univ., Nara (Japan). Dept. of Chemistry

    1998-10-01

    It has been unsuccessful to solve a set of time-dependent Schroedinger equations numerically for many-body quantum systems which involve, e.g., a number of hydrogen molecules, protons, and excess electrons at a low temperature, where quantum effect evidently appears. This undesirable situation is fatal for the investigation of real low-temperature chemical systems because they are essentially composed of many quantum degrees of freedom. However, if we use a new technique called `path integral centroid molecular dynamics (CMD) simulation` proposed by Cao and Voth in 1994, the real-time semi-classical dynamics of many degrees of freedom can be computed by utilizing the techniques already developed in the traditional classical molecular dynamics (MD) simulations. Therefore, the CMD simulation is expected to be very powerful tool for the quantum dynamics studies or real substances. (J.P.N.)

  5. Communication: Molecular dynamics and {sup 1}H NMR of n-hexane in liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Weber, Adrian C. J., E-mail: WeberA@BrandonU.CA [Chemistry Department, Brandon University, 270-18th Street, Brandon, Manitoba R7A 6A9 (Canada); Burnell, E. Elliott, E-mail: elliott.burnell@ubc.ca [Chemistry Department, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1 (Canada); Meerts, W. Leo, E-mail: leo.meerts@science.ru.nl [Radboud University, Institute for Molecules and Materials, Heyendaalseweg 135, NL-6525 AJ Nijmegen (Netherlands); Atomic, Molecular and Laser Physics, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Lange, Cornelis A. de, E-mail: c.a.de.lange@vu.nl [Atomic, Molecular and Laser Physics, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Dong, Ronald Y., E-mail: rondong@phas.ubc.ca [Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, British Columbia V6T 1Z1 (Canada); Muccioli, Luca, E-mail: Luca.Muccioli@unibo.it; Pizzirusso, Antonio, E-mail: Antonio.Pizzirusso80@gmail.com; Zannoni, Claudio, E-mail: Claudio.Zannoni@unibo.it [Dipartimento di Chimica Industriale “Toso Montanari,” Università di Bologna and INSTM, viale Risorgimento 4, 40136 Bologna (Italy)

    2015-07-07

    The NMR spectrum of n-hexane orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy (CMA-ES). The spectrum contains over 150 000 transitions, with many sharp features appearing above a broad, underlying background signal that results from the plethora of overlapping transitions from the n-hexane as well as from the liquid crystal. The CMA-ES requires initial search ranges for NMR spectral parameters, notably the direct dipolar couplings. Several sets of such ranges were utilized, including three from MD simulations and others from the modified chord model that is specifically designed to predict hydrocarbon-chain dipolar couplings. In the end, only inaccurate dipolar couplings from an earlier study utilizing proton-proton double quantum 2D-NMR techniques on partially deuterated n-hexane provided the necessary estimates. The precise set of dipolar couplings obtained can now be used to investigate conformational averaging of n-hexane in a nematic environment.

  6. Molecular reorientations in a substance with liquid-crystalline and plastic-crystalline phases

    International Nuclear Information System (INIS)

    Nguyen, Xuan Phuc.

    1986-05-01

    Results of dielectric relaxation (DR), quasielastic neutron scattering (QNS), far infrared absorption (FIR), proton magnetic resonance (PMR), differential scanning calorimetry (DSC) and preliminary X-ray diffraction measurements on the di-n-pentyloxyazoxybenzene (5.OAOB) are presented. The measurements carried out by all these methods showed that 5.OAOB exhibits a nontypical for liquid-crystalline materials phase diagram. It has two mesophases: a nematic (N) and an ''intermediate'' crystalline phase just below it. A complex interpretation of results obtained is given. All suggestions concerning the character of reorientational motions of the molecule as a whole as well as of its segments in mesomorphic phases are analyzed. From comparison of the DR and QNS studies one can conclude that in the N phase the molecule as a whole performs rotational diffusion around the long axis (τ DR ∼ 100 ps) and at the same time the two moieties perform faster independent reorientations around N - benzene rings bonds withτ QNS ∼ 5 ps. On the basis of various experimental data it is shown that the CrI phase is a plastic-crystalline phase for which the molecule and its segments perform fast stochastic unaxial reorientations. This is the first case where the existence of such a phase in liquid-crystalline materials has been experimentally confirmed. (author)

  7. High-Resolution Liquid Chromatography Tandem Mass Spectrometry Enables Large Scale Molecular Characterization of Dissolved Organic Matter

    Directory of Open Access Journals (Sweden)

    Daniel Petras

    2017-12-01

    Full Text Available Dissolved organic matter (DOM is arguably one of the most complex exometabolomes on earth, and is comprised of thousands of compounds, that together contribute more than 600 × 1015 g carbon. This reservoir is primarily the product of interactions between the upper ocean's microbial food web, yet abiotic processes that occur over millennia have also modified many of its molecules. The compounds within this reservoir play important roles in determining the rate and extent of element exchange between inorganic reservoirs and the marine biosphere, while also mediating microbe-microbe interactions. As such, there has been a widespread effort to characterize DOM using high-resolution analytical methods including nuclear magnetic resonance spectroscopy (NMR and mass spectrometry (MS. To date, molecular information in DOM has been primarily obtained through calculated molecular formulas from exact mass. This approach has the advantage of being non-targeted, accessing the inherent complexity of DOM. Molecular structures are however still elusive and the most commonly used instruments are costly. More recently, tandem mass spectrometry has been employed to more precisely identify DOM components through comparison to library mass spectra. Here we describe a data acquisition and analysis workflow that expands the repertoire of high-resolution analytical approaches available to access the complexity of DOM molecules that are amenable to electrospray ionization (ESI MS. We couple liquid chromatographic separation with tandem MS (LC-MS/MS and a data analysis pipeline, that integrates peak extraction from extracted ion chromatograms (XIC, molecular formula calculation and molecular networking. This provides more precise structural characterization. Although only around 1% of detectable DOM compounds can be annotated through publicly available spectral libraries, community-wide participation in populating and annotating DOM datasets could rapidly increase the

  8. Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: from boiling point to glass transition temperature.

    Science.gov (United States)

    Schmidtke, B; Petzold, N; Kahlau, R; Rössler, E A

    2013-08-28

    We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10(-12) s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature T(g) is covered. We focus on low-T(g) liquids for which the high-temperature limit τ ≅ 10(-12) s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" E(coop)(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)]. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a E(coop)(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

  9. Diagnostic performance of automated liquid culture and molecular line probe assay in smear-negative pulmonary tuberculosis.

    Science.gov (United States)

    Kotwal, Aarti; Biswas, Debasis; Raghuvanshi, Shailendra; Sindhwani, Girish; Kakati, Barnali; Sharma, Shweta

    2017-04-01

    The diagnosis of smear-negative pulmonary tuberculosis (PTB) is particularly challenging, and automated liquid culture and molecular line probe assays (LPA) may prove particularly useful. The objective of our study was to evaluate the diagnostic potential of automated liquid culture (ALC) technology and commercial LPA in sputum smear-negative PTB suspects. Spot sputum samples were collected from 145 chest-symptomatic smear-negative patients and subjected to ALC, direct drug susceptibility test (DST) testing and LPA, as per manufacturers' instructions. A diagnostic yield of 26.2% was observed among sputum smear-negative TB suspects with 47.4% of the culture isolates being either INH- and/or rifampicin-resistant. Complete agreement was observed between the results of ALC assay and LPA except for two isolates which demonstrated sensitivity to INH and rifampicin at direct DST but were rifampicin-resistant in LPA. Two novel mutations were also detected among the multidrug isolates by LPA. In view of the diagnostic challenges associated with the diagnosis of TB in sputum smear-negative patients, our study demonstrates the applicability of ALC and LPA in establishing diagnostic evidence of TB.

  10. Vibrational signatures of cation-anion hydrogen bonding in ionic liquids: a periodic density functional theory and molecular dynamics study.

    Science.gov (United States)

    Mondal, Anirban; Balasubramanian, Sundaram

    2015-02-05

    Hydrogen bonding in alkylammonium based protic ionic liquids was studied using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Normal-mode analysis within the harmonic approximation and power spectra of velocity autocorrelation functions were used as tools to obtain the vibrational spectra in both the gas phase and the crystalline phases of these protic ionic liquids. The hydrogen bond vibrational modes were identified in the 150-240 cm(-1) region of the far-infrared (far-IR) spectra. A blue shift in the far-IR mode was observed with an increasing number of hydrogen-bonding sites on the cation; the exact peak position is modulated by the cation-anion hydrogen bond strength. Sub-100 cm(-1) bands in the far-IR spectrum are assigned to the rattling motion of the anions. Calculated NMR chemical shifts of the acidic protons in the crystalline phase of these salts also exhibit the signature of cation-anion hydrogen bonding.

  11. Molecular dynamics simulation studies of mid-size liquid n-Alkanes, C12–C160

    International Nuclear Information System (INIS)

    Kwon, Tae Woo; Lee, Song Hi

    2015-01-01

    In this study, we report the results of molecular dynamics simulations (MD) for model systems of mid-size liquid n-alkanes (C 12 –C 160 ) at several temperatures (⁓2700 K) in canonical ensembles to calculate structural and dynamic properties (viscosity η, self-diffusion constant D, and monomeric friction constant ζ). For the small n-alkanes for n ≤ 80, the chains are clearly ≥ 1, which leads to the conclusion that the liquid n-alkanes are far away from the Rouse regime, but for the n-alkanes for n ≥ 120, the chains are ⁓ 1 and they are Gaussian. It is found that the long chains of these n-alkanes at high temperatures show abnormalities in density, viscosity, and monomeric friction constant. The mass and temperature dependences of structural and dynamic properties (η, D, and ζ) are discussed

  12. Experimental investigations on prototype heat storage units utilizing stable supercooling of sodium acetate trihydrate mixtures

    DEFF Research Database (Denmark)

    Dannemand, Mark; Dragsted, Janne; Fan, Jianhua

    2016-01-01

    Laboratory tests of two heat storage units based on the principle of stable supercooling of sodium acetate trihydrate (SAT) mixtures were carried out. One unit was filled with 199.5 kg of SAT with 9% extra water to avoid phase separation of the incongruently melting salt hydrate. The other unit...

  13. Crystallization in diblock copolymer thin films at different degrees of supercooling

    DEFF Research Database (Denmark)

    Darko, C.; Botiz, I.; Reiter, G.

    2009-01-01

    The crystalline structures in thin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low and interme...

  14. Contact freezing of supercooled cloud droplets on collision with mineral dust particles: effect of particle size

    Science.gov (United States)

    Hoffmann, Nadine; Duft, Denis; Kiselev, Alexei; Leisner, Thomas

    2013-04-01

    The contact freezing of supercooled cloud droplets is one of the potentially important and the least investigated heterogeneous mechanism of ice formation in the tropospheric clouds [1]. On the time scales of cloud lifetime the freezing of supercooled water droplets via contact mechanism may occur at higher temperature compared to the same IN immersed in the droplet. However, the laboratory experiments of contact freezing are very challenging due to the number of factors affecting the probability of ice formation. In our experiment we study single water droplets freely levitated in the laminar flow of mineral dust particles acting as the contact freezing nuclei. By repeating the freezing experiment sufficient number of times we are able to reproduce statistical freezing behavior of large ensembles of supercooled droplets and measure the average rate of freezing events. We show that the rate of freezing at given temperature is governed only by the rate of droplet -particle collision and by the properties of the contact ice nuclei. In this contribution we investigate the relationship between the freezing probability and the size of mineral dust particle (represented by illite) and show that their IN efficiency scales with the particle size. Based on this observation, we discuss the similarity between the freezing of supercooled water droplets in immersion and contact modes and possible mechanisms of apparent enhancement of the contact freezing efficiency. [1] - K.C. Young, The role of contact nucleation in ice phase initiation in clouds, Journal of the Atmospheric Sciences 31, 1974

  15. Endogenous and exogenous ice-nucleating agents constrain supercooling in the hatchling painted turtle.

    Science.gov (United States)

    Costanzo, Jon P; Baker, Patrick J; Dinkelacker, Stephen A; Lee, Richard E

    2003-02-01

    Hatchlings of the painted turtle (Chrysemys picta) commonly hibernate in their shallow, natal nests. Survival at temperatures below the limit of freeze tolerance (approximately -4 degrees C) apparently depends on their ability to remain supercooled, and, whereas previous studies have reported that supercooling capacity improves markedly with cold acclimation, the mechanistic basis for this change is incompletely understood. We report that the crystallization temperature (T(c)) of recently hatched (summer) turtles acclimated to 22 degrees C and reared on a substratum of vermiculite or nesting soil was approximately 5 degrees C higher than the T(c) determined for turtles acclimated to 4 degrees C and tested in winter. This increase in supercooling capacity coincided with elimination of substratum (and, in fewer cases, eggshell) that the hatchlings had ingested; however, this association was not necessarily causal because turtles reared on a paper-covered substratum did not ingest exogenous matter but nevertheless showed a similar increase in supercooling capacity. Our results for turtles reared on paper revealed that seasonal development of supercooling capacity fundamentally requires elimination of ice-nucleating agents (INA) of endogenous origin: summer turtles, but not winter turtles, produced feces (perhaps derived from residual yolk) that expressed ice-nucleating activity. Ingestion of vermiculite or eggshell, which had modest ice-nucleating activity, had no effect on the T(c), whereas ingestion of nesting soil, which contained two classes of potent INA, markedly reduced the supercooling capacity of summer turtles. This effect persisted long after the turtles had purged their guts of soil particles, because the T(c) of winter turtles reared on nesting soil (mean +/- S.E.M.=-11.6+/-1.4 degrees C) was approximately 6 degrees C higher than the T(c) of winter turtles reared on vermiculite or paper. Experiments in which winter turtles were fed INA commonly found in

  16. Chain length effects on the vibrational structure and molecular interactions in the liquid normal alkyl alcohols

    Science.gov (United States)

    Kiefer, Johannes; Wagenfeld, Sabine; Kerlé, Daniela

    2018-01-01

    Alkyl alcohols are widely used in academia, industry, and our everyday lives, e.g. as cleaning agents and solvents. Vibrational spectroscopy is commonly used to identify and quantify these compounds, but also to study their structure and behavior. However, a comprehensive investigation and comparison of all normal alkanols that are liquid at room temperature has not been performed, surprisingly. This study aims at bridging this gap with a combined experimental and computational effort. For this purpose, the alkyl alcohols from methanol to undecan-1-ol have been analyzed using infrared and Raman spectroscopy. A detailed assignment of the individual peaks is presented and the influence of the alkyl chain length on the hydrogen bonding network is discussed. A 2D vibrational mapping allows a straightforward visualization of the effects. The conclusions drawn from the experimental data are backed up with results from Monte Carlo simulations using the simulation package Cassandra.

  17. Influence of Nanoparticles and Graphite Foam on the Supercooling of Acetamide

    International Nuclear Information System (INIS)

    Yu, J.; Chen, X.; Ma, X.; Song, Q.; Zhao, Y.; Cao, J.

    2014-01-01

    Acetamide is a promising phase change materials (PCMs) for thermal storage,but the large supercooling during the freezing process has limited its application. In this study, we prepared acetamide-SiO 2 composites by adding nano-SiO 2 into acetamide. This modified PCM was then impregnated into the porous graphite foam forming acetamide-SiO 2 -graphite foam form-stable composites. These composites were subjected to melting-solidification cycles 50 times; the time-temperature curves were tracked and recorded during these cycles. The time-temperature curves showed that, for the acetamide containing 2 wt. % SiO 2 , the supercooling phenomenon was eliminated and the material’s performance was stable for 50 cycles. The solidification temperature of the acetamide-SiO 2 -graphite foam samples was 65°C and the melting temperature was lowered to 65°C. The samples exhibited almost no supercooling and the presence of SiO 2 had no significant effect on the melting-solidification temperature. The microscopic supercooling of the acetamide-SiO 2 composite was measured using differential scanning calorimetry (DSC). The results indicated that when the content of SiO 2 was 1 wt. to 2 wt. %, the supercooling could be reduced to less than 10°C and heat was sufficiently released during solidification. Finally, a set of algorithms was derived using MATLAB software for simulating the crystallization of samples based on the classical nucleation theory. The results of the simulation agreed with the experiment results.

  18. Influence of Nanoparticles and Graphite Foam on the Supercooling of Acetamide

    Directory of Open Access Journals (Sweden)

    Jia Yu

    2014-01-01

    Full Text Available Acetamide is a promising phase change materials (PCMs for thermal storage,but the large supercooling during the freezing process has limited its application. In this study, we prepared acetamide-SiO2 composites by adding nano-SiO2 into acetamide. This modified PCM was then impregnated into the porous graphite foam forming acetamide-SiO2-graphite foam form-stable composites. These composites were subjected to melting-solidification cycles 50 times; the time-temperature curves were tracked and recorded during these cycles. The time-temperature curves showed that, for the acetamide containing 2 wt. % SiO2, the supercooling phenomenon was eliminated and the material’s performance was stable for 50 cycles. The solidification temperature of the acetamide-SiO2-graphite foam samples was 65°C and the melting temperature was lowered to 65°C. The samples exhibited almost no supercooling and the presence of SiO2 had no significant effect on the melting-solidification temperature. The microscopic supercooling of the acetamide-SiO2 composite was measured using differential scanning calorimetry (DSC. The results indicated that when the content of SiO2 was 1 wt. to 2 wt. %, the supercooling could be reduced to less than 10°C and heat was sufficiently released during solidification. Finally, a set of algorithms was derived using MATLAB software for simulating the crystallization of samples based on the classical nucleation theory. The results of the simulation agreed with the experiment results.

  19. Fabrication and characterization of microencapsulated phase change material with low supercooling for thermal energy storage

    International Nuclear Information System (INIS)

    Tang, Xiaofen; Li, Wei; Zhang, Xingxiang; Shi, Haifeng

    2014-01-01

    Microencapsulated phase change material with a low supercooling degree is one of the increasing important researches as well as industrial application for thermal energy storage. This study develops a novel and low supercooling microencapsulated n-octadecane (MicroC18) with n-octadecyl methacrylate (ODMA)–methacrylic acid (MAA) copolymer as shell using suspension-like polymerization. The fabrication and properties of MicroC18 were characterized by using a field-emission scanning electron microscope (FE-SEM), Fourier transformed infrared spectroscopy (FTIR), particle size distribution analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The MicroC18 with spherical shapes and an average diameter of 1.60–1.68 μm are fabricated. The onset crystallizing temperatures of MicroC18 are only 4 °C below that of n-octadecane. The unique copolymer shell has a significant impact on the low supercooling of MicroC18. The n-octadecane in all of the samples crystalizes by heterogeneous nucleation. The content of n-octadecane in the microcapsules is low; however, the microcapsules still exhibit high enthalpy through the contribution of the shells. At a monomers/n-octadecane mass ratio is 2:1, as used in the recipes, the MicroC18 with highest phase change enthalpy was obtained. The temperature of thermal resistant of MicroC18 is approximately 235.6 °C, which is affected by the thickness of the polymer shell. - Highlights: • Microencapsulated n-octadecane with comb-like copolymer shell has low supercooling. • The unique shell plays a significant role in suppressing supercooling. • The types of cross-linker affect morphologies and heat enthalpies of microcapsules. • Microcapsules exhibit high phase change enthalpies and thermal stabilities

  20. Shock wave energy dissipation behavior (SWED) in Network forming ionic liquids (NILs): A Molecular dynamics study

    Science.gov (United States)

    Guda Vishnu, Karthik; Strachan, Alejandro

    2017-06-01

    SWED materials play a crucial role in protecting both personnel and structures in close proximity to blasts or ballistic impact. Exposure to shock waves with intensities as low as 1 MPa can cause brain injury in personnel and, hence, it is extremely important to understand the mechanisms operating in SWED materials and help design improved formulations. Recent experimental studies show that NILs containing di-ammonium cations and citrate anions with glass transition temperatures (Tg) below room temperature exhibit shockwave absorption characteristics that outperform polyurea (PU), a benchmark SWED assessment material. The experimentalists further hypothesized that the increased SWED ability in NILs with longer side chains (in di-ammonium cation) is due to a permanent structural ordering and nano-scale segregation. We use molecular dynamics simulations with the Dreiding force field to study shock propagation mechanisms in NILs. Shock propagation mechanisms in these materials are explored by performing both Hugoniostat and large scale non-equilibrium molecular dynamics (NEMD) simulations at 300 K. The simulation results show that the NIL 5-6 (5 C atoms (back bone) and 6 C atoms (side chain)) attenuates shocks better than NIL 5-3 (3 C atoms (side chain) and higher Tg) and PMMA in agreement with experimental observation. The simulations show that under shock loading the structures lose long range order; we find no evidence of nano-segregation nor or permanent structural changes.

  1. Sequence-dependent separation of trinucleotides by ion-interaction reversed-phase liquid chromatography A structure-retention study assisted by soft-modelling and molecular dynamics

    Czech Academy of Sciences Publication Activity Database

    Mikulášek, K.; Jaroň, Kamil S.; Kulhánek, P.; Bittová, M.; Havliš, J.

    2016-01-01

    Roč. 1469, October (2016), s. 88-95 ISSN 0021-9673 Institutional support: RVO:68081766 Keywords : Sequence-dependent separation * Ion-interaction reversed-phase liquid chromatography * Trinucleotides * Oligonucleotide sequence isomers * QSRR * Molecular dynamics Subject RIV: CE - Biochemistry Impact factor: 3.981, year: 2016

  2. Kinetics of iron redox reactions in silicate liquids: A high-temperature X-ray absorption and Raman spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); CEA VALRHO Marcoule, SCDV, LEBV, BP 17171, 30207 Bagnols/Ceze (France); Neuville, D.R. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France)]. E-mail: neuville@ipgp.jussieu.fr; Cormier, L. [IMPMC, CNRS UMR 7590, Universites Paris 6 and 7 and IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); Roux, J. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France); Hazemann, J.-L. [Laboratoire de cristallographie, UPR 5031, CNRS, 38043 Grenoble (France); Pinet, O. [CEA VALRHO Marcoule, SCDV, LEBV, BP 17171, 30207 Bagnols/Ceze (France); Richet, P. [Physique des Mineraux et Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris cedex 05 (France)

    2006-06-30

    The oxidation kinetics of a Fe-bearing supercooled liquid of the system SiO{sub 2}-CaO-MgO-Na{sub 2}O-FeO has been determined near the glass transition range by X-ray absorption near edge structure (XANES) and Raman spectroscopies. Both techniques yield room-temperature iron redox ratios in accord with wet chemical, Moessbauer and electron microprobe analyses. Similar oxidation kinetics have also been observed with both methods. At constant temperature, the kinetics obey an exponential law with a characteristic time that follows an Arrhenian temperature dependence. As redox changes are too fast to be accounted for in terms of diffusion of either ionic or molecular oxygen, these results lend further support to the idea that the rate-limiting factor for oxidation near the glass transition is diffusion of network-modifying cations along with a flux of electron holes.

  3. Liquid-phase characterization of molecular interactions in polyunsaturated and n-fatty acid methyl esters by (1)H low-field nuclear magnetic resonance.

    Science.gov (United States)

    Meiri, Nitzan; Berman, Paula; Colnago, Luiz Alberto; Moraes, Tiago Bueno; Linder, Charles; Wiesman, Zeev

    2015-01-01

    To identify and develop the best renewable and low carbon footprint biodiesel substitutes for petroleum diesel, the properties of different biodiesel candidates should be studied and characterized with respect to molecular structures versus biodiesel liquid property relationships. In our previous paper, (1)H low-field nuclear magnetic resonance (LF-NMR) relaxometry was investigated as a tool for studying the liquid-phase molecular packing interactions and morphology of fatty acid methyl esters (FAMEs). The technological potential was demonstrated with oleic acid and methyl oleate standards having similar alkyl chains but different head groups. In the present work, molecular organization versus segmental and translational movements of FAMEs in their pure liquid phase, with different alkyl chain lengths (10-20 carbons) and degrees of unsaturation (0-3 double bonds), were studied with (1)H LF-NMR relaxometry and X-ray, (1)H LF-NMR diffusiometry, and (13)C high-field NMR. Based on density values and X-ray measurements, it was proposed that FAMEs possess a liquid crystal-like order above their melting point, consisting of random liquid crystal aggregates with void spaces between them, whose morphological properties depend on chain length and degree of unsaturation. FAMEs were also found to exhibit different degrees of rotational and translational motions, which were rationalized by chain organization within the clusters, and the degree and type of molecular interactions and temperature effects. At equivalent fixed temperature differences from melting point, saturated FAME molecules were found to have similar translational motion regardless of chain length, expressed by viscosity, self-diffusion coefficients, and spin-spin (T 2) (1)H LF-NMR. T 2 distributions suggest increased alkyl chain rigidity, and reduced temperature response of the peaks' relative contribution with increasing unsaturation is a direct result of the alkyl chain's morphological packing and molecular

  4. Molecular dynamics simulations for transport coefficients of liquid argon: new approaches

    International Nuclear Information System (INIS)

    Lee, Song Hi; Park, Dong Kue; Kang, Dae Bok

    2003-01-01

    The stress and the heat-flux auto-correlation functions in the Green-Kubo formulas for shear viscosity and thermal conductivity have non-decaying long-time tails. This problem can be overcome by improving the statistical accuracy by N (number of particles)times, considering the stress and the heat-flux of the system as properties of each particle. The mean square stress and the heat-flux displacements in the Einstein formulas for shear viscosity and thermal conductivity are non linear functions of time since the quantities in the mean square stress and the heat-flux displacements are not continuous under periodic boundary conditions. An alternative to these quantities is to integrate the stress and the heat-flux with respect to time, but the resulting mean square stress and heat-flux displacements are still not linear versus time. This problem can be also overcome by improving the statistical accuracy. The results for transport coefficients of liquid argon obtained are discussed

  5. Influence of temperature and molecular structure on ionic liquid solvation layers.

    Science.gov (United States)

    Wakeham, Deborah; Hayes, Robert; Warr, Gregory G; Atkin, Rob

    2009-04-30

    Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.

  6. Bottom-up derivation of conservative and dissipative interactions for coarse-grained molecular liquids with the conditional reversible work method

    International Nuclear Information System (INIS)

    Deichmann, Gregor; Marcon, Valentina; Vegt, Nico F. A. van der

    2014-01-01

    Molecular simulations of soft matter systems have been performed in recent years using a variety of systematically coarse-grained models. With these models, structural or thermodynamic properties can be quite accurately represented while the prediction of dynamic properties remains difficult, especially for multi-component systems. In this work, we use constraint molecular dynamics simulations for calculating dissipative pair forces which are used together with conditional reversible work (CRW) conservative forces in dissipative particle dynamics (DPD) simulations. The combined CRW-DPD approach aims to extend the representability of CRW models to dynamic properties and uses a bottom-up approach. Dissipative pair forces are derived from fluctuations of the direct atomistic forces between mapped groups. The conservative CRW potential is obtained from a similar series of constraint dynamics simulations and represents the reversible work performed to couple the direct atomistic interactions between the mapped atom groups. Neopentane, tetrachloromethane, cyclohexane, and n-hexane have been considered as model systems. These molecular liquids are simulated with atomistic molecular dynamics, coarse-grained molecular dynamics, and DPD. We find that the CRW-DPD models reproduce the liquid structure and diffusive dynamics of the liquid systems in reasonable agreement with the atomistic models when using single-site mapping schemes with beads containing five or six heavy atoms. For a two-site representation of n-hexane (3 carbons per bead), time scale separation can no longer be assumed and the DPD approach consequently fails to reproduce the atomistic dynamics

  7. Bottom-up derivation of conservative and dissipative interactions for coarse-grained molecular liquids with the conditional reversible work method

    Energy Technology Data Exchange (ETDEWEB)

    Deichmann, Gregor; Marcon, Valentina; Vegt, Nico F. A. van der, E-mail: vandervegt@csi.tu-darmstadt.de [Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Straße 10, 64287 Darmstadt (Germany)

    2014-12-14

    Molecular simulations of soft matter systems have been performed in recent years using a variety of systematically coarse-grained models. With these models, structural or thermodynamic properties can be quite accurately represented while the prediction of dynamic properties remains difficult, especially for multi-component systems. In this work, we use constraint molecular dynamics simulations for calculating dissipative pair forces which are used together with conditional reversible work (CRW) conservative forces in dissipative particle dynamics (DPD) simulations. The combined CRW-DPD approach aims to extend the representability of CRW models to dynamic properties and uses a bottom-up approach. Dissipative pair forces are derived from fluctuations of the direct atomistic forces between mapped groups. The conservative CRW potential is obtained from a similar series of constraint dynamics simulations and represents the reversible work performed to couple the direct atomistic interactions between the mapped atom groups. Neopentane, tetrachloromethane, cyclohexane, and n-hexane have been considered as model systems. These molecular liquids are simulated with atomistic molecular dynamics, coarse-grained molecular dynamics, and DPD. We find that the CRW-DPD models reproduce the liquid structure and diffusive dynamics of the liquid systems in reasonable agreement with the atomistic models when using single-site mapping schemes with beads containing five or six heavy atoms. For a two-site representation of n-hexane (3 carbons per bead), time scale separation can no longer be assumed and the DPD approach consequently fails to reproduce the atomistic dynamics.

  8. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II

    Science.gov (United States)

    Limmer, David T.; Chandler, David

    2013-06-01

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys. 135, 134503 (2011), 10.1063/1.3643333 and preprint arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light.

  9. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II

    International Nuclear Information System (INIS)

    Limmer, David T.; Chandler, David

    2013-01-01

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys.135, 134503 (2011) and preprint http://arxiv.org/abs/arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light

  10. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II

    Energy Technology Data Exchange (ETDEWEB)

    Limmer, David T.; Chandler, David, E-mail: chandler@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States)

    2013-06-07

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys.135, 134503 (2011) and preprint http://arxiv.org/abs/arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light.

  11. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. II.

    Science.gov (United States)

    Limmer, David T; Chandler, David

    2013-06-07

    This paper extends our earlier studies of free energy functions of density and crystalline order parameters for models of supercooled water, which allows us to examine the possibility of two distinct metastable liquid phases [D. T. Limmer and D. Chandler, J. Chem. Phys. 135, 134503 (2011) and preprint arXiv:1107.0337 (2011)]. Low-temperature reversible free energy surfaces of several different atomistic models are computed: mW water, TIP4P/2005 water, Stillinger-Weber silicon, and ST2 water, the last of these comparing three different treatments of long-ranged forces. In each case, we show that there is one stable or metastable liquid phase, and there is an ice-like crystal phase. The time scales for crystallization in these systems far exceed those of structural relaxation in the supercooled metastable liquid. We show how this wide separation in time scales produces an illusion of a low-temperature liquid-liquid transition. The phenomenon suggesting metastability of two distinct liquid phases is actually coarsening of the ordered ice-like phase, which we elucidate using both analytical theory and computer simulation. For the latter, we describe robust methods for computing reversible free energy surfaces, and we consider effects of electrostatic boundary conditions. We show that sensible alterations of models and boundary conditions produce no qualitative changes in low-temperature phase behaviors of these systems, only marginal changes in equations of state. On the other hand, we show that altering sampling time scales can produce large and qualitative non-equilibrium effects. Recent reports of evidence of a liquid-liquid critical point in computer simulations of supercooled water are considered in this light.

  12. Sputtering of silicon and glass substrates with polyatomic molecular ion beams generated from ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Takeuchi, Mitsuaki, E-mail: m-takeuchi@kuee.kyoto-u.ac.jp; Hoshide, Yuki; Ryuto, Hiromichi; Takaoka, Gikan H. [Photonics and Electronics Science and Engineering Center, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2016-03-15

    The effect of irradiating 1-ethyl-3-methylimidazolium positive (EMIM{sup +}) or dicyanamide negative (DCA{sup –}) ion beams using an ionic liquid ion source was characterized concerning its sputtering properties for single crystalline Si(100) and nonalkaline borosilicate glass substrates. The irradiation of the DCA{sup –} ion beam onto the Si substrate at an acceleration voltage of 4 and 6 kV exhibited detectable sputtered depths greater than a couple of nanometers with an ion fluence of only 1 × 10{sup 15} ions/cm{sup 2}, while the EMIM{sup +} ion beam produced the same depths with an ion fluence 5 × 10{sup 15} ions/cm{sup 2}. The irradiation of a 4 kV DCA{sup –} ion beam at a fluence of 1 × 10{sup 16} ions/cm{sup 2} also yields large etching depths in Si substrates, corresponding to a sputtering yield of Si/DCA{sup – }= 10, and exhibits a smoothed surface roughness of 0.05 nm. The interaction between DCA{sup –} and Si likely causes a chemical reaction that relates to the high sputtering yield and forms an amorphous C-N capping layer that results in the smooth surface. Moreover, sputtering damage by the DCA{sup –} irradiation, which was estimated by Rutherford backscattering spectroscopy with the channeling technique, was minimal compared to Ar{sup +} irradiation at the same condition. In contrast, the glass substrates exhibited no apparent change in surface roughnesses when sputtered by the DCA{sup –} irradiation compared to the unirradiated glass substrates.

  13. Formation, structure, and evolution of boiling nucleus and interfacial tension between bulk liquid phase and nucleus

    Science.gov (United States)

    Wang, Xiao-Dong; Peng, Xiao-Feng; Tian, Yong; Wang, Bu-Xuan

    2005-05-01

    In this paper, the concept of the molecular free path is introduced to derive a criterion distinguishing active molecules from inactive molecules in liquid phase. A concept of the critical aggregation concentration (CAC) of active molecules is proposed to describe the physical configuration before the formation of a nucleus during vapor-liquid phase transition. All active molecules exist as monomers when the concentration of active molecules is lower than CAC, while the active molecules will generate aggregation once the concentration of the active molecules reaches CAC. However, these aggregates with aggregation number, N, smaller than five can steadily exist in bulk phase. The other excess active molecules can only produce infinite aggregation and form a critical nucleus of vapor-liquid phase transition. Without any outer perturbation the state point of CAC corresponds to the critical superheated or supercooled state. Meanwhile, a model of two-region structure of a nucleus is proposed to describe nucleus evolution. The interfacial tension between bulk liquid phase and nucleus is dependent of the density gradient in the transition region and varies with the structure change of the transition region. With the interfacial tension calculated using this model, the predicted nucleation rate is very close to the experimental measurement. Furthermore, this model and associated analysis provides solid theoretical evidences to clarify the definition of nucleation rate and understand nucleation phenomenon with the insight into the physical nature.

  14. Comparison of molecular models of carbon monoxide for calculation of vapor-liquid equilibrium

    Directory of Open Access Journals (Sweden)

    Bibian Alonso Hoyos-Madrigal

    2015-01-01

    Full Text Available Existen varios modelos moleculares para el monóxido de carbono desarrollados a partir de diferentes mediciones experimentales. El objetivo de este trabajo es comparar los resultados que varios de estos modelos producen en el cálculo del equilibrio líquido-vapor en busca de recomendar qué modelo debe ser usado de acuerdo la propiedad y la fase que se desea calcular. Los modelos seleccionados corresponden a cuatro modelos no polares, con uno o dos sitios Lennard-Jones, y cuatro modelos polares, con dipolos o cargas parciales para representar la polaridad del monóxido de carbono. Simulaciones Monte Carlo en la versión Gibbs canónica (NVT-GEMC se emplearon para determinar las densidades de las fases en equilibrio, la presión de vapor y la entalpia de vaporización entre 80 y 130 K con cada uno de los modelos seleccionados. Se encontró que los modelos más complejos SVH, ANC y PGB, son los que mejor describen la densidad del líquido saturado (alrededor de 7% de desviación promedio, pero estos modelos generan desviaciones mayores al 40% para las propiedades del vapor y al 20% para la entalpia de vaporización. Por otro lado, el modelo no- polar BLF generó las menores desviaciones para la presión de saturación y la densidad del vapor (6.8 y 21.5%, respectivamente. Este modelo, al igual que el modelo HCB, produce desviaciones aceptables para la densidad del líquido y la entalpia de vaporización (entre 10 y 12%. Los modelos no polares BLF y HCB, que no requieren el cálculo de las interacciones de largo alcance, se pueden considerar como los modelos moleculares que presentan un balance satisfactorio entre desviaciones en los resultados y complejidad de cálculo.

  15. Structure in sheared supercooled liquids: Dynamical rearrangements of an effective system of icosahedra.

    Science.gov (United States)

    Pinney, Rhiannon; Liverpool, Tanniemola B; Royall, C Patrick

    2016-12-21

    We consider a binary Lennard-Jones glassformer whose super-Arrhenius dynamics are correlated with the formation of particles organized into icosahedra under simple steady state shear. We recast this glassformer as an effective system of icosahedra [Pinney et al., J. Chem. Phys. 143, 244507 (2015)]. From the observed population of icosahedra in each steady state, we obtain an effective temperature which is linearly dependent on the shear rate in the range considered. Upon shear banding, the system separates into a region of high shear rate and a region of low shear rate. The effective temperatures obtained in each case show that the low shear regions correspond to a significantly lower temperature than the high shear regions. Taking a weighted average of the effective temperature of these regions (weight determined by region size) yields an estimate of the effective temperature which compares well with an effective temperature based on the global mesocluster population of the whole system.

  16. Crystallization Kinetics of Supercooled Liquid Ge-Sb Based on Ultrafast Calorimetry

    NARCIS (Netherlands)

    Chen, Bin; Momand, Jamo; Vermeulen, Paul A.; Kooi, Bart J.

    The crystallization kinetics of phase-change materials (PCMs) entails a crucial aspect of phase-change memory technology, and their study is also of interest to advance the understanding of crystallization in general. Research on crystallization of PCMs remains challenging because of the short

  17. Mapping of low molecular weight heparins using reversed phase ion pair liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Li, Daoyuan; Chi, Lequan; Jin, Lan; Xu, Xiaohui; Du, Xuzhao; Ji, Shengli; Chi, Lianli

    2014-01-01

    Low molecular weight heparins (LMWHs) are structurally complex, highly sulfated and negatively charged, linear carbohydrate polymers prepared by chemical or enzymatic depolymerization of heparin. They are widely used as anticoagulant drugs possessing better bioavailability, longer half-life, and lower side effects than heparin. Comprehensive structure characterization of LMWHs is important for drug quality assurance, generic drug application, and new drug research and development. However, fully characterization of all oligosaccharide chains in LMWHs is not feasible for current available analytical technologies due to their structure complexity and heterogeneity. Fingerprinting profiling is an efficient way for LMWHs' characterization and comparison. In this work, we present a simple, sensitive, and powerful analytical approach for structural characterization of LMWHs. Two different LMWHs, enoxaparin and nadroparin, were analyzed using reversed phase ion pair electrospray ionization mass spectrometry (RPIP-ESI-MS). More than 200 components were identified, including major structures, minor structures, and process related impurities. This approach is robust for high resolution and complementary fingerprinting analysis of LMWHs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Molecular Biosensors for Electrochemical Detection of Infectious Pathogens in Liquid Biopsies: Current Trends and Challenges.

    Science.gov (United States)

    Campuzano, Susana; Yáñez-Sedeño, Paloma; Pingarrón, José Manuel

    2017-11-03

    Rapid and reliable diagnosis of infectious diseases caused by pathogens, and timely initiation of appropriate treatment are critical determinants to promote optimal clinical outcomes and general public health. Conventional in vitro diagnostics for infectious diseases are time-consuming and require centralized laboratories, experienced personnel and bulky equipment. Recent advances in electrochemical affinity biosensors have demonstrated to surpass conventional standards in regards to time, simplicity, accuracy and cost in this field. The tremendous potential offered by electrochemical affinity biosensors to detect on-site infectious pathogens at clinically relevant levels in scarcely treated body fluids is clearly stated in this review. The development and application of selected examples using different specific receptors, assay formats and electrochemical approaches focusing on the determination of specific circulating biomarkers of different molecular (genetic, regulatory and functional) levels associated with bacterial and viral pathogens are critically discussed. Existing challenges still to be addressed and future directions in this rapidly advancing and highly interesting field are also briefly pointed out.

  19. A molecular theory of smectic C liquid crystals made of rod-like molecules.

    Science.gov (United States)

    Govind, A S; Madhusudana, N V

    2002-10-01

    Organic compounds exhibiting the smectic C phase are made of rod-like molecules that have dipolar groups with lateral components. We argue that the off-axis character of the lateral dipolar groups can account for tilt in layered smectics (SmC, SmC*, SmI etc.). We develop a mean-field theory of the smectic C phase based on a single-particle potential of the form UC is proportional to sin(2theta) cos phi, consistent with the biaxial nature of the phase, where theta and phi are the polar and azimuthal angles, respectively. The hard-rod interactions that favour the smectic A phase with zero tilt angle are also included. The theoretical phase diagrams compare favourably with experimental trends. Our theory also leads to the following results: i) a first-order smectic C to smectic A transition above some value of the McMillan parameter alpha, leading to a tricritical point on the smectic C to smectic A transition line and ii) a first-order smectic C to smectic C transition over a very small range of values of the model parameters. We have also extended the theory to include the next higher-order term in the tilting potential and to include the effect of different tilt angles for the molecular core and the chain in the SmC phase.

  20. A molecular dynamics examination of the relationship between self-diffusion and viscosity in liquid metals

    Science.gov (United States)

    Lü, Yongjun; Cheng, Hao; Chen, Min

    2012-06-01

    The self-diffusion coefficients D and the viscosities η of elemental Ni, Cu, and Ni-Si alloys have been calculated over a wide temperature range by molecular dynamics simulations. For elemental Ni and Cu, Arrhenius-law variations of D and η with temperature dominate. The temperature dependence of Dη can be approximated by a linear relation, whereas the Stokes-Einstein relation is violated. The calculations of D and η are extended to the regions close to the crystallization of Ni95Si5, Ni90Si10, and the glass transitions of Ni80Si20 and Ni75Si25. The results show that both D and η strongly deviate from the Arrhenius law in the vicinity of phase transitions, exhibiting a power-law divergence. We find a decoupling of diffusion and viscous flow just above the crystallization of Ni95Si5 and Ni90Si10. For the two glass-forming alloys, Ni80Si20 and Ni75Si25, the relation Dη = const is obeyed as the glass transition is approached, indicating a dynamic coupling as predicted by the mode-coupling theory. This coupling is enhanced with increasing Si composition and at 25%, Si spans a wide temperature range through the melting point. The decoupling is found to be related to the distribution of local ordered structure in the melts. The power-law governing the growth of solid-like clusters prior to crystallization creates a dynamic heterogeneity responsible for decoupling.

  1. Synchronized Molecular-Dynamics simulation for thermal lubrication of a polymeric liquid between parallel plates

    Science.gov (United States)

    Yasuda, Shugo; Yamamoto, Ryoichi

    2015-11-01

    The Synchronized Molecular-Dynamics simulation which was recently proposed by authors is applied to the analysis of polymer lubrication between parallel plates. In the SMD method, the MD simulations are assigned to small fluid elements to calculate the local stresses and temperatures and are synchronized at certain time intervals to satisfy the macroscopic heat- and momentum-transport equations.The rheological properties and conformation of the polymer chains coupled with local viscous heating are investigated with a non-dimensional parameter, the Nahme-Griffith number, which is defined as the ratio of the viscous heating to the thermal conduction at the characteristic temperature required to sufficiently change the viscosity. The present simulation demonstrates that strong shear thinning and a transitional behavior of the conformation of the polymer chains are exhibited with a rapid temperature rise when the Nahme-Griffith number exceeds unity.The results also clarify that the reentrant transition of the linear stress-optical relation occurs for large shear stresses due to the coupling of the conformation of polymer chains with heat generation under shear flows. This study was financially supported by JSPS KAKENHI Grant Nos. 26790080 and 26247069.

  2. Magnetic, electric and optic properties of liquid crystals

    International Nuclear Information System (INIS)

    Florea, St.C.

    1980-01-01

    We study the nematic liquid crystals of thermotrop type. We also studied the crystals whose mesomorphism occured both at temperature increasing and decreasing and during the supercooling phase (monotrope). Investigation results performed by us have had in view the following: clearing up and experimental support of a new mechanism of nuclear relaxation in liquid crystals, proposed by author; usage of experimental techniques and methods for to characterize and test some mesomorph media used in very important applications, such as color TV. (author)

  3. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.; Varela, Luis M., E-mail: luismiguel.varela@usc.es [Grupo de Nanomateriais e Materia Branda, Departamento de Física da Materia Condensada, Universidade de Santiago de Compostela, Campus Vida s/n, E-15782 Santiago de Compostela (Spain); Cabeza, Oscar [Facultade de Ciencias, Universidade da Coruña, Campus A Zapateira s/n, E-15008 A Coruña (Spain); Fedorov, Maxim [Department of Physics, Scottish University Physics Alliance (SUPA), University of Strathclyde, John Anderson Bldg., 107 Rottenrow East, Glasgow G4 0NG (United Kingdom); Lynden-Bell, Ruth M. [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom)

    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 of 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

  4. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    International Nuclear Information System (INIS)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.; Varela, Luis M.; Cabeza, Oscar; Fedorov, Maxim; Lynden-Bell, Ruth M.

    2015-01-01

    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 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 of 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 3 ] − and [PF 6 ] − 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 2+ cations. No qualitative

  5. SHORT COMMUNICATION: Recognition of supercooled dew in a quartz crystal microbalance dew-point sensor by slip phenomena

    Science.gov (United States)

    Kwon, Su-Yong; Kim, Jong-Chul; Choi, Byung-Il

    2007-10-01

    Distinguishing between a supercooled dew and frost below 0 °C in dew/frost-point measurements is an important and challenging problem that has not yet been completely solved. This study presents a new method for the recognition of a supercooled dew in a dew/frost-point sensor. A quartz crystal microbalance (QCM) sensor was used as a dew/frost-point sensor to detect a dew and a supercooled dew as well as frost. The slip phenomenon occurring at an interface between the water droplet and the surface of the quartz crystal resonator of the QCM sensor gives a simple and accurate way of distinguishing between a supercooled dew and frost below 0 °C. This method can give a highly accurate measurement of the dew or the frost point without misreading in the dew-point sensor at temperatures below 0 °C.

  6. Molecular aspect ratio and anchoring strength effects in a confined Gay-Berne liquid crystal

    Science.gov (United States)

    Cañeda-Guzmán, E.; Moreno-Razo, J. A.; Díaz-Herrera, E.; Sambriski, E. J.

    2014-04-01

    Phase diagrams for Gay-Berne (GB) fluids were obtained from molecular dynamics simulations for GB(2, 5, 1, 2) (i.e. short mesogens) and GB(3, 5, 1, 2) (i.e. long mesogens), which yield isotropic, nematic, and smectic-B phases. The long-mesogen fluid also yields the smectic-A phase. Ordered phases of the long-mesogen fluid form at higher temperatures and lower densities when compared to those of the short-mesogen fluid. The effect of confinement under weak and strong substrate couplings in slab geometry was investigated. Compared to the bulk, the isotropic-nematic transition does not shift in temprature significantly for the weakly coupled substrate in either mesogen fluid. However, the strongly coupled substrate shifts the transition to lower temperature. Confinement induces marked stratification in the short-mesogen fluid. This effect diminishes with distance from the substrate, yielding bulk-like behaviour in the slab central region. Fluid stratification is very weak for the long-mesogen fluid, but the strongly coupled substrate induces 'smectisation', an ordering effect that decays with distance. Orientation of the fluid on the substrate depends on the mesogen. There is no preferred orientation in a plane parallel to the substrate for the weakly coupled case. In the strongly coupled case, the mesogen orientation mimics that of adjacent fluid layers. Planar anchoring is observed with a broad distribution of orientations in the weakly coupled case. In the strongly coupled case, the distribution leans toward planar orientations for the short-mesogen fluid, while a marginal preference for tilting persists in the long-mesogen fluid.

  7. Molecular dynamics investigation of nanoscale substrate topography and its interaction with liquids

    Science.gov (United States)

    Cordeiro Rodrigues, Jhonatam

    Nanotechnology has been presenting successful applications in several areas. However, experimentation with nanoscale materials is costly and limited in analysis capability. This research investigates the use of molecular dynamics (MD) simulations to model and study nanomaterials and manufacturing processes. MD simulations are employed to reduce cost, optimize design, increase productivity and allow for the investigation of material interactions not yet observable through experimentation. This work investigates the interaction of water with substrates at the nanoscale. The effect of temperature, droplet impingement velocities and size, as well as substrate material, are investigated at the nanoscale. Several substrate topography designs were modeled to reveal their influence on the wettability of the substrate. Nanoscale gold and silicon substrates are more hydrophilic at higher temperatures than at room temperature. The reduction in droplet diameter increases its wettability. High impingement velocity of droplets does not influence final wettability of substrates but induces higher diffusion rates of droplets in a heated environment. Droplets deposited over a gradient of surface exposure presents spontaneous movement. The Leidenfrost effect was investigated at the nanoscale. Droplets of 4 and 10nm in diameter presented behaviors pertinent to the Leidenfrost effect at 373K, significantly lower than at micro scale and of potential impact to the field. Topographical features were manipulated using superhydrophobic coating resulting in micro whiskers. Nanoimprint lithography (NIL) was used to manufacture substrate topographies at the nanoscale. Water droplets were deposited on the substrates and their wettability was measured using droplet contact angles. Lower surface area exposure resulted in higher contact angles. The experimental relationships between surface topography and substrate wettability were used to validate the insights gained from MD simulations for

  8. Activity and conformation of lysozyme in molecular solvents, protic ionic liquids (PILs) and salt-water systems.

    Science.gov (United States)

    Wijaya, Emmy C; Separovic, Frances; Drummond, Calum J; Greaves, Tamar L

    2016-09-21

    Improving protein stabilisation is important for the further development of many applications in the pharmaceutical, specialty chemical, consumer product and agricultural sectors. However, protein stabilization is highly dependent on the solvent environment and, hence, it is very complex to tailor protein-solvent combinations for stable protein maintenance. Understanding solvent features that govern protein stabilization will enable selection or design of suitable media with favourable solution environments to retain protein native conformation. In this work the structural conformation and activity of lysozyme in 29 solvent systems were investigated to determine the role of various solvent features on the stability of the enzyme. The solvent systems consisted of 19 low molecular weight polar solvents and 4 protic ionic liquids (PILs), both at different water content levels, and 6 aqueous salt solutions. Small angle X-ray scattering, Fourier transform infrared spectroscopy and UV-vis spectroscopy were used to investigate the tertiary and secondary structure of lysozyme along with the corresponding activity in various solvation systems. At low non-aqueous solvent concentrations (high water content), the presence of solvents and salts generally maintained lysozyme in its native structure and enhanced its activity. Due to the presence of a net surface charge on lysozyme, electrostatic interactions in PIL-water systems and salt solutions enhanced lysozyme activity more than the specific hydrogen-bond interactions present in non-ionic molecular solvents. At higher solvent concentrations (lower water content), solvents with a propensity to exhibit the solvophobic effect, analogous to the hydrophobic effect in water, retained lysozyme native conformation and activity. This solvophobic effect was observed particularly for solvents which contained hydroxyl moieties. Preferential solvophobic effects along with bulky chemical structures were postulated to result in less

  9. Frequency-dependent local field factors in dielectric liquids by a polarizable force field and molecular dynamics simulations

    International Nuclear Information System (INIS)

    Davari, Nazanin; Haghdani, Shokouh; Åstrand, Per-Olof

    2015-01-01

    A force field model for calculating local field factors, i.e. the linear response of the local electric field for example at a nucleus in a molecule with respect to an applied electric field, is discussed. It is based on a combined charge-transfer and point-dipole interaction model for the polarizability, and thereby it includes two physically distinct terms for describing electronic polarization: changes in atomic charges arising from transfer of charge between the atoms and atomic induced dipole moments. A time dependence is included both for the atomic charges and the atomic dipole moments and if they are assumed to oscillate with the same frequency as the applied electric field, a model for frequency-dependent properties are obtained. Furthermore, if a life-time of excited states are included, a model for the complex frequency-dependent polariability is obtained including also information about excited states and the absorption spectrum. We thus present a model for the frequency-dependent local field factors through the first molecular excitation energy. It is combined with molecular dynamics simulations of liquids where a large set of configurations are sampled and for which local field factors are calculated. We are normally not interested in the average of the local field factor but rather in configurations where it is as high as possible. In electrical insulation, we would like to avoid high local field factors to reduce the risk for electrical breakdown, whereas for example in surface-enhanced Raman spectroscopy, high local field factors are desired to give dramatically increased intensities

  10. Molecular Dynamics Simulations on the solvation and interfacial behaviour of hydrophobic species. Applications to the TATB hypothesis and to the liquid/liquid extraction of cations to supercritical CO2

    International Nuclear Information System (INIS)

    Schurhammer, R.

    2001-12-01

    We report molecular dynamics studies on the solvation of charged hydrophobic molecules in pure liquids and at liquid / liquid interfaces. The first part of the thesis deals with the TATB hypothesis according to which the Asφ 4 + (TA + ) and Bφ 4 - (TB - ) ions have the same free energy of solvation in any solvent. The two ions are found to be solvated differently in pure liquids (water, chloroform, acetonitrile) as at a chloroform / water interface. These results are confirmed by free energy calculations and by simulations on iso-volume spherical S + and S - ions, which perfectly meet the TATB criteria. The many methodological tests performed show the importance of (i) the corrected treatment of 'long range interactions' (ii) the precise repartition of atomic charges (iii) the solvent models, especially for water, on the + / - charge discrimination by solvent. In the second part, in relation to the liquid / liquid extraction of cations from water to supercritical CO 2 , we report the behaviour of ions (Cs + , UO 2 2+ , Eu 3+ ), of un-complexed extractants molecules (tri-n-butylphosphate, calixarene), of their complexes with the cations and nitric acid at a preformed chloroform / water interface and during de-mixing simulations which started from a perfectly mixed CO 2 / water solutions. These studies demonstrate the importance of interfacial phenomena, of simulation conditions and acid and extractant concentrations, in assisted ion extraction to supercritical CO 2 . (author)

  11. Algorithms for GPU-based molecular dynamics simulations of complex fluids: Applications to water, mixtures, and liquid crystals.

    Science.gov (United States)

    Kazachenko, Sergey; Giovinazzo, Mark; Hall, Kyle Wm; Cann, Natalie M

    2015-09-15

    A custom code for molecular dynamics simulations has been designed to run on CUDA-enabled NVIDIA graphics processing units (GPUs). The double-precision code simulates multicomponent fluids, with intramolecular and intermolecular forces, coarse-grained and atomistic models, holonomic constraints, Nosé-Hoover thermostats, and the generation of distribution functions. Algorithms to compute Lennard-Jones and Gay-Berne interactions, and the electrostatic force using Ewald summations, are discussed. A neighbor list is introduced to improve scaling with respect to system size. Three test systems are examined: SPC/E water; an n-hexane/2-propanol mixture; and a liquid crystal mesogen, 2-(4-butyloxyphenyl)-5-octyloxypyrimidine. Code performance is analyzed for each system. With one GPU, a 33-119 fold increase in performance is achieved compared with the serial code while the use of two GPUs leads to a 69-287 fold improvement and three GPUs yield a 101-377 fold speedup. © 2015 Wiley Periodicals, Inc.

  12. Observed mechanism for the breakup of small bundles of cellulose Iα and Iβ in ionic liquids from molecular dynamics simulations.

    Science.gov (United States)

    Rabideau, Brooks D; Agarwal, Animesh; Ismail, Ahmed E

    2013-04-04

    Explicit, all-atom molecular dynamics simulations are used to study the breakup of small bundles of cellulose Iα and Iβ in the ionic liquids [BMIM]Cl, [EMIM]Ac, and [DMIM]DMP. In all cases, significant breakup of the bundles is observed with the initial breakup following a common underlying mechanism. Anions bind strongly to the hydroxyl groups of the exterior strands of the bundle, forming negatively charged complexes. Binding also weakens the intrastrand hydrogen bonds present in the cellulose strands, providing greater strand flexibility. Cations then intercalate between the individual strands, likely due to charge imbalances, providing the bulk to push the individual moieties apart and initiating the separation. The peeling of an individual strand from the main bundle is observed in [EMIM]Ac with an analysis of its hydrogen bonds with other strands showing that the chain detaches glucan by glucan from the main bundle in discrete, rapid events. Further analysis shows that the intrastrand hydrogen bonds of each glucan tend to break for a sustained period of time before the interstrand hydrogen bonds break and strand detachment occurs. Examination of similar nonpeeling strands shows that, without this intrastrand hydrogen bond breakage, the structural rigidity of the individual unit can hinder its peeling despite interstrand hydrogen bond breakage.

  13. Comparison of two protic ionic liquid behaviors in the presence of an electric field using molecular dynamics

    Science.gov (United States)

    Mehta, Neil A.; Levin, Deborah A.

    2017-12-01

    The effects of an external electric field on two ionic liquids (ILs) are investigated using molecular dynamics electrospray simulations of ethylammonium nitrate (EAN) and ethanolammonium nitrate (EOAN). In the absence of an external electric field, long alkyl chains were observed in EAN but not in EOAN. When the electric field was applied, the anions of both ILs formed a barrier along the applied field, but only in EAN did this barrier result in a static bilayer composed of two parallel layers of cations and anions. The primary hydrogen bonds (HBs) connecting the EAN cations and anions were formed between the ammonium and the nitrate groups. In contrast, they were formed between the ammonium as well as the hydroxyl groups and the nitrate groups in EOAN. The applied electric field was found effective in reducing the number of O1-HO⋯O type HBs but was less effective against the N-HN⋯O type HBs. It was observed that the N-C1-CM backbone angles of EAN allowed for greater storage of the energy supplied by the electric field in the form of torsional degree of freedom compared to the N-C1-CM angles of EOAN. The combination of stronger HBs and higher energy storage in the N-C1-CM covalent angle in EAN results in a stronger resistance of ion emission from the bulk compared to EOAN.

  14. Gradual crossover in molecular organization of stable liquid H2O at moderately high pressure and temperature

    DEFF Research Database (Denmark)

    Koga, Yoshikata; Westh, Peter; Yoshida, Koh

    2014-01-01

    temperature. The extrapolated temperature to zero p seems to be about 70 – 80 °C for points X and 90 – 110 °C for Y. Furthermore, the mid-points of X and Y seem to extrapolate to the triple point of liquid, ice Ih and ice III. Recalling that the zero x Gly extrapolation of point X and Y for binary aqueous...... of the step named point X and its end point Y. In analogy with another third and fourth derivative pair in binary aqueous solutions of glycerol, dα p /dx Gly and d2 α p /dx Gly 2, at 0.1 MPa (α p is the thermal expansivity and x Gly the mole fraction of solute glycerol) in our recent publication [J. Solution...... Chem. 43, 663-674 (2014); DOI:10.1007/s10953-013-0122-7], we argue that there is a gradual crossover in the molecular organization of pure H2O from a low to a high p-regions starting at point X and ending at Y at a fixed T. The crossover takes place gradually spanning for about 100 MPa at a fixed...

  15. Fast and General Method To Predict the Physicochemical Properties of Druglike Molecules Using the Integral Equation Theory of Molecular Liquids.

    Science.gov (United States)

    Palmer, David S; Mišin, Maksim; Fedorov, Maxim V; Llinas, Antonio

    2015-09-08

    We report a method to predict physicochemical properties of druglike molecules using a classical statistical mechanics based solvent model combined with machine learning. The RISM-MOL-INF method introduced here provides an accurate technique to characterize solvation and desolvation processes based on solute-solvent correlation functions computed by the 1D reference interaction site model of the integral equation theory of molecular liquids. These functions can be obtained in a matter of minutes for most small organic and druglike molecules using existing software (RISM-MOL) (Sergiievskyi, V. P.; Hackbusch, W.; Fedorov, M. V. J. Comput. Chem. 2011, 32, 1982-1992). Predictions of caco-2 cell permeability and hydration free energy obtained using the RISM-MOL-INF method are shown to be more accurate than the state-of-the-art tools for benchmark data sets. Due to the importance of solvation and desolvation effects in biological systems, it is anticipated that the RISM-MOL-INF approach will find many applications in biophysical and biomedical property prediction.

  16. Structure and dynamics of biomembranes in room-temperature ionic liquid water solutions studied by neutron scattering and by molecular dynamics simulations

    Science.gov (United States)

    Benedetto, Antonio; Ballone, Pietro

    2018-05-01

    Increasing attention is being devoted to the interaction of a new class of organic ionic liquids known as room-temperature ionic liquids (RTILs) with biomolecules, partly because of health and environment concerns, and, even more, for the prospect of exciting new applications in biomedicine, sensing and energy technologies. Here we focus on the interaction between RTILs and phospholipid bilayers that are well-accepted models for bio-membranes. We discuss how neutron scattering has been used to probe both the structure and the dynamics of these systems, and how its integration with molecular dynamics simulation has allowed the determination of the microscopic details of their interaction.

  17. On abnormal decomposition of supercooled austenite in carbon and alloy steels

    International Nuclear Information System (INIS)

    Parusov, V.V.; Dolzhenkov, I.I.; Podobedov, L.V.; Vakulenko, I.A.

    1980-01-01

    Residual stresses which appear as a result of thermal cycling in the temperature range of 300-700 deg C are investigated in an austenitic class steel (03Kh18N11) to ground the assumption on the effect of plastic deformation, appearing due to thermal stresses, on the mechanism of supercooled austenite decomposition. The determination of residual stresses is carried out with the help of X-ray diffraction analysis. It is established that the deformation brings about an increase in density of dislocation the interaction of which leads to the formation of a typical austenite substructure which conditions the proceeding of the eutectoid transformation according to an abnormal mechanism. It is noted, that the grain pearlite formation due to plastic and microplastic deformation of supercooled austenite induced by thermal stresses should be taken into account when developing steel heat treatment shedules [ru

  18. Resonant inelastic X-ray scattering of liquid water

    International Nuclear Information System (INIS)

    Nilsson, Anders; Tokushima, Takashi; Horikawa, Yuka; Harada, Yoshihisa; Ljungberg, Mathias P.; Shin, Shik; Pettersson, Lars G.M.

    2013-01-01

    Highlights: ► Two peaks are observed in the lone pair region of the XES spectrum of water assigned to tetrahedral and distorted hydrogen bonding configurations. ► The isotope effect observed as different relative peak heights is due to spectral line shape differences. ► The two different hydrogen bonding environments can be related to local structures mimicking either low density water or high density water. -- Abstract: We review recent studies using resonant inelastic X-ray scattering (RIXS) or also here denoted X-ray emission spectroscopy (XES) on liquid water and the assignment of the two sharp peaks in the lone-pair region. Using the excitation energy dependence we connect the two peaks to specific features in the X-ray absorption (XAS) spectrum which have independently been assigned to molecules in tetrahedral or distorted configurations. The polarization dependence shows that both peaks are of 1b 1 origin supporting an interpretation in terms of two structural species, tetrahedral or disordered, which is furthermore consistent with the temperature-dependence of the two peaks. We discuss effects of life-time vibrational interference and how this affects the two components differently and also leads to differences in the relative peak heights for H 2 O and D 2 O. We show furthermore that the inherent structure in molecular dynamics simulations contain the structural bimodality suggested by XES, but this is smeared out in the real structure when temperature is included. We present a discussion around alternative interpretations suggesting that the origin of the two peaks is related to ultrafast dissociation and show evidence that such a model is inconsistent with several experimental observations and theoretical concepts. We conclude that the peaks reflect a temperature-dependent balance in fluctuations between tetrahedral and disordered structures in the liquid. This is well-aligned with theories of water under supercooled conditions and higher pressures

  19. Resonant inelastic X-ray scattering of liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Nilsson, Anders, E-mail: nilsson@slac.stanford.edu [SUNCAT Ctr Interface Sci and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (United States); Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (United States); Department of Physics, AlbaNova University Center, Stockholm University, SE-10691 (Sweden); Tokushima, Takashi [RIKEN/Spring-8, Sayo-cho, Sayo, Hyogo 679-5148 (Japan); Horikawa, Yuka [RIKEN/Spring-8, Sayo-cho, Sayo, Hyogo 679-5148 (Japan); Institute for Solid State Physics (ISSP), The University of Tokyo, Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan); Harada, Yoshihisa [RIKEN/Spring-8, Sayo-cho, Sayo, Hyogo 679-5148 (Japan); Institute for Solid State Physics (ISSP), The University of Tokyo, Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan); Synchrotron Radiation Research Organization, The University of Tokyo, Sayo-cho, Sayo, Hyogo 679-5165 (Japan); Ljungberg, Mathias P. [Department of Physics, AlbaNova University Center, Stockholm University, SE-10691 (Sweden); Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193 Bellaterra (Spain); Shin, Shik [RIKEN/Spring-8, Sayo-cho, Sayo, Hyogo 679-5148 (Japan); Institute for Solid State Physics (ISSP), The University of Tokyo, Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan); Synchrotron Radiation Research Organization, The University of Tokyo, Sayo-cho, Sayo, Hyogo 679-5165 (Japan); Pettersson, Lars G.M. [Department of Physics, AlbaNova University Center, Stockholm University, SE-10691 (Sweden)

    2013-06-15

    Highlights: ► Two peaks are observed in the lone pair region of the XES spectrum of water assigned to tetrahedral and distorted hydrogen bonding configurations. ► The isotope effect observed as different relative peak heights is due to spectral line shape differences. ► The two different hydrogen bonding environments can be related to local structures mimicking either low density water or high density water. -- Abstract: We review recent studies using resonant inelastic X-ray scattering (RIXS) or also here denoted X-ray emission spectroscopy (XES) on liquid water and the assignment of the two sharp peaks in the lone-pair region. Using the excitation energy dependence we connect the two peaks to specific features in the X-ray absorption (XAS) spectrum which have independently been assigned to molecules in tetrahedral or distorted configurations. The polarization dependence shows that both peaks are of 1b{sub 1} origin supporting an interpretation in terms of two structural species, tetrahedral or disordered, which is furthermore consistent with the temperature-dependence of the two peaks. We discuss effects of life-time vibrational interference and how this affects the two components differently and also leads to differences in the relative peak heights for H{sub 2}O and D{sub 2}O. We show furthermore that the inherent structure in molecular dynamics simulations contain the structural bimodality suggested by XES, but this is smeared out in the real structure when temperature is included. We present a discussion around alternative interpretations suggesting that the origin of the two peaks is related to ultrafast dissociation and show evidence that such a model is inconsistent with several experimental observations and theoretical concepts. We conclude that the peaks reflect a temperature-dependent balance in fluctuations between tetrahedral and disordered structures in the liquid. This is well-aligned with theories of water under supercooled conditions and

  20. The relationship between gut contents and supercooling capacity in hatchling painted turtles (Chrysemys picta).

    Science.gov (United States)

    Packard, Gary C; Packard, Mary J

    2006-05-01

    Painted turtles (Chrysemys picta) typically spend their first winter of life in a shallow, subterranean hibernaculum (the natal nest) where they seemingly withstand exposure to ice and cold by resisting freezing and becoming supercooled. However, turtles ingest soil and fragments of eggshell as they are hatching from their eggs, and the ingestate usually contains efficient nucleating agents that cause water to freeze at high subzero temperatures. Consequently, neonatal painted turtles have only a modest ability to undergo supercooling in the period immediately after hatching. We studied the limit for supercooling (SCP) in hatchlings that were acclimating to different thermal regimes and then related SCPs of the turtles to the amount of particulate matter in their gastrointestinal (GI) tract. Turtles that were transferred directly from 26 degrees C (the incubation temperature) to 2 degrees C did not purge soil from their gut, and SCPs for these animals remained near -4 degrees C for the 60 days of the study. Animals that were held at 26 degrees C for the duration of the experiment usually cleared soil from their GI tract within 24 days, but SCPs for these turtles were only slightly lower after 60 days than they were at the outset of the experiment. Hatchlings that were acclimating slowly to 2 degrees C cleared soil from their gut within 24 days and realized a modest reduction in their SCP. However, the limit of supercooling in the slowly acclimating animals continued to decline even after all particulate material had been removed from their GI tract, thereby indicating that factors intrinsic to the nucleating agents themselves also may have been involved in the acclimation of hatchlings to low temperature. The lowest SCPs for turtles that were acclimating slowly to 2 degrees C were similar to SCPs recorded in an earlier study of animals taken from natural nests in late autumn, so the current findings affirm the importance of seasonally declining temperatures in