Glassy dynamics in a liquid of anisotropic molecules: Bifurcation of relaxation spectrum.

In experimental and theoretical studies of glass transition phenomena, one often finds a sharp crossover in dynamical properties at a temperature Tcr. A bifurcation of a relaxation spectrum is also observed at a temperature TB≈Tcr; both lie significantly above the glass transition temperature. In order to better understand these phenomena, we introduce a new model of glass-forming liquids, a binary mixture of prolate and oblate ellipsoids. This model system exhibits sharp thermodynamic and dynamic anomalies, such as the specific heat jump during heating and a sharp variation in the thermal expansion coefficient around a temperature identified as the glass transition temperature, Tg. The same temperature is obtained from the fit of the calculated relaxation times to the Vogel-Fulcher-Tammann (VFT) form. As the temperature is lowered, the calculated single peak rotational relaxation spectrum splits into two peaks at TB above the estimated Tg. Similar bifurcation is also observed in the distribution of short-to-intermediate time translational diffusion. Interrogation of the two peaks reveals a lower extent of dynamic heterogeneity in the population of the faster mode. We observe an unexpected appearance of a sharp peak in the product of rotational relaxation time τ2 and diffusion constant D at a temperature Tcr, close to TB, but above the glass transition temperature. Additionally, we coarse-grain the system into cubic boxes, each containing, on average, ∼62 particles, to study the average dynamical properties. Clear evidence of large-scale sudden changes in the diffusion coefficient and rotational correlation time signals first-order transitions between low and high-mobility domains.

Microscopic origin of breakdown of Stokes-Einstein relation in binary mixtures: Inherent structure analysis.

Aqueous binary mixtures often exhibit dramatic departure from the predicted hydrodynamic behavior when transport properties are plotted against composition. We show by inherent structure (IS) analysis that this sharp composition dependent breakdown of the Stokes-Einstein relation can be attributed to the non-monotonic variation in the average inherent structure energy of these mixtures. Further IS analysis reveals the existence of a unique ground state, stabilized by both the formation of an optimum number of H-bonds and a favorable hydrophobic interaction at this composition. The surprisingly sharp turnaround behavior observed in the effective hydrodynamic radius also owes its origin to the same combination of these two factors. Interestingly, the temperature dependence of isothermal compressibility shows a minimum at the particular composition. Extensive studies on water-dimethyl sulfoxide and water-ethanol mixtures using two different force-fields of water reveal many features that are nearly universal. A justification of this quasi-universal behavior is provided in terms of a mode-coupling theory (MCT) of viscosity, which can serve as the starting point of a remarkable correlation observed with the nearest neighbor structure, as captured by the first peaks of the radial distribution function, and the slowdown in the intermediate scattering function at intermediate wavenumbers. Therefore, the formation of the local structure captured through IS analysis can be correlated with the MCT.

Anomalous viscoelastic response of water-dimethyl sulfoxide solution and a molecular explanation of non-monotonic composition dependence of viscosity.

Amphiphilic molecules such as dimethyl sulfoxide (DMSO) and its aqueous binary mixtures exhibit pronounced nonideality in composition dependence of several static and dynamic properties. We carry out detailed molecular dynamics simulations to calculate various properties including viscosity of the mixture and combine the results with a mode coupling theory analysis to show that this nonideality can be attributed to local structures that are stable on a short time scale but transient on a long time scale to maintain the large scale homogeneity of the solution. Although the existence of such quasistable structures has been deciphered from spectroscopy, a detailed characterization does not exist. We calculate stress-stress autocorrelation functions (SACFs) of water-DMSO binary mixtures. We employ two different models of water, SPC/E and TIP4P/2005, to check the consistency of our results. Viscosity shows a pronounced nonmonotonic composition dependence. The calculated values are in good agreement with the experimental results. Fourier transform of SACF provides frequency-dependent viscosity. The frequency-dependent viscosity (that is, viscoelasticity) is also found to be strongly dependent on composition. Viscoelasticity exhibits sharp peaks due to intramolecular vibrational modes of DMSO, which are also seen in the density of states. We evaluate the wavenumber dependent dynamic structure factor and wavenumber dependent relaxation time. The latter also exhibits a sharp nonmonotonic composition dependence. The calculated dynamic structure factor is used in mode coupling theory expression of viscosity to obtain a semiquantitative understanding of anomalous composition dependence of viscosity. Both the self-diffusion coefficients and rotational correlation times of water and DMSO molecules exhibit nonmonotonic composition dependence.

Three-stage phase separation kinetics in a model liquid binary mixture: A computational study.

We study microscopic aspects of initial phase separation through atomistic molecular dynamics simulation of a structure breaking liquid binary mixture. We find that the phase separation kinetics in a fluid binary mixture model system can indeed be unusual. It can be fast, with a crossover from a pronounced exponential to non-exponential and non-linear dynamics. An important outcome of this work is the quantification of time scales involved in phase separation kinetics at an early stage. The initial exponential phase separation is complete within ∼100 ps. The initial phase separation involves aggregation of small droplets that form rapidly after the quench. This is followed by segregation that gives rise to pattern formation with multiple bands of segregated species. During this initial phase, a particle is found to have moved only about ∼5 molecular diameters. The next stage is slower and characterized by break-up and disappearance of small islands of species trapped inside the domains of other species of the binary mixture. The phase separation in this second stage is highly non-exponential and power-law-like. We identify a new feature in the very late stage of phase separation kinetics that seems to have eluded previous attention, the smoothing of the rugged interface between the two species. This is opposite to the roughening transition one finds on the surface of solids in contact with its vapor phase. The present atomistic simulation provides a molecular picture in terms of molecular motions and displacements.

Dynamics of linear molecules in water: Translation-rotation coupling in jump motion driven diffusion.

We study by computer simulations, and by theory, the coupled rotational and translational dynamics of three important linear diatomic molecules, namely, carbon monoxide (CO), nitric oxide (NO), and cyanide ion (CN-) in water. Translational diffusion of these molecules is found to be strongly coupled to their own rotational dynamics which, in turn, are coupled to similar motions of the surrounding water. In particular, we find that coupled orientational jump motions play an important role in all three cases. While CO and NO show similar features, CN- exhibits certain differences. Our results agree well with the known experimental values of the diffusion coefficient. We examined the validity of hydrodynamic predictions and found them to be inadequate, particularly for rotational diffusion. A mode coupling theory approach is developed and applied to understand the complexity of translation-rotation coupling.

Dynamics of a binary mixture of non-spherical molecules: Test of hydrodynamic predictions.

We consider a new class of model systems to study systematically the role of molecular shape in the transport properties of dense liquids. Our model is a liquid binary mixture where both the molecules are non-spherical and characterized by a collection of parameters. Although in the real world most of the molecules are non-spherical, only a limited number of theoretical studies exist on the effects of molecular shapes and hardly any have addressed the validity of the hydrodynamic predictions of rotational and translational diffusion of these shapes in liquids. In this work, we study a model liquid consisting of a mixture of prolate and oblate (80:20 mixture) ellipsoids with interactions governed by a modified Gay-Berne potential for a particular aspect ratio (ratio of the length and diameter of the ellipsoids), at various temperature and pressure conditions. We report calculations of transport properties of this binary mixture by varying temperature over a wide range at a fixed pressure. We find that for the pressure-density conditions studied, there is no signature of any phase separation, except transitions to the crystalline phase at low temperatures and relatively low pressure (the reason we largely confined our studies to high pressure). We find that for our model binary mixture, both stick and slip hydrodynamic predictions break down in a major fashion, for both prolates and oblates and particularly so for rotation. Moreover, prolates and oblates themselves display different dynamical features in the mean square displacement and in orientational time correlation functions.

Psychological profile of multi drug resistance TB patients: A qualitative study from a Tertiary care Centre of Kolkata.

INTRODUCTION: There has been a new challenge to the already existing threat of tuberculosis (TB) and that is drug resistance TB (DR-TB). The causal relationships between mental disorders and TB are complicated and relatively unexplored. For this reason a qualitative study was done on DR-TB patients attending R G Kar Medical College. MATERIALS AND METHODS: The study population consisted of the patients who are registered for the DR-TB regimen are followed up four times with General Health Questionnaire (GHQ). Those scoring poorly were sent for expert evaluation by psychologist, who counselled them, and followed them up after in-depth interviews. These records of in-depth interview were analysed as qualitative research inputs. RESULTS: In our study out of 165 patients, (4.8%) needed interventions. The domains emerging from the study are worried about future and as well as family, disbelief about the diagnosis, embarrassment regarding the diagnosis, fear of death, blaming fate for the disease, stigma, suicidal ideation. CONCLUSION: This study finds out the important domains of psychogical problems among the patients and also advocates a psychologist to remain at DR-TB centres.

Solid-liquid transition in polydisperse Lennard-Jones systems.

We study melting of a face-centered crystalline solid consisting of polydisperse Lennard-Jones spheres with Gaussian polydispersity in size. The phase diagram reproduces the existence of a nearly temperature invariant terminal polydispersity (δ(t) =/~ 0.11), with no signature of reentrant melting. The absence of reentrant melting can be attributed to the influence of the attractive part of the potential upon melting. We find that at terminal polydispersity the fractional density change approaches zero, which seems to arise from vanishingly small compressibility of the disordered phase. At constant temperature and volume fraction the system undergoes a sharp transition from crystalline solid to the disordered amorphous or fluid state with increasing polydispersity. This has been quantified by second- and third-order rotational invariant bond orientational order, as well as by the average inherent structure energy. The translational order parameter also indicates a similar sharp structural change at δ =/~ 0.09 in case of T(*) = 1.0, φ = 0.58. The free energy calculation further supports the sharp nature of the transition. The third-order rotationally invariant bond order shows that with increasing polydispersity, the local cluster favors a more icosahedral arrangement and the system loses its local crystalline symmetry. Interestingly, the value of structure factor S(k) of the amorphous phase at δ =/~ 0.10 (just beyond the solid-liquid transition density at T(*) = 1) becomes 2.75, which is below the value of 2.85 required for freezing given by the empirical Hansen-Verlet rule of crystallization, well known in the theory of freezing.

Inherent structures of phase-separating binary mixtures: nucleation, spinodal decomposition, and pattern formation.

An energy landscape view of phase separation and nonideality in binary mixtures is developed by exploring their potential energy landscape (PEL) as functions of temperature and composition. We employ molecular dynamics simulations to study a model that promotes structure breaking in the solute-solvent parent binary liquid, at low temperatures. The PEL of the system captures the potential energy distribution of the inherent structures (IS) of the system and is obtained by removing the kinetic energy (including that of intermolecular vibrations). The broader distribution of the inherent structure energy for structure breaking liquid than that of the structure making liquid demonstrates the larger role of entropy in stabilizing the parent liquid of the structure breaking type of binary mixtures. At high temperature, although the parent structure of the structure breaking binary mixture is homogenous, the corresponding inherent structure is found to be always phase separated, with a density pattern that exhibits marked correlation with the energy of its inherent structure. Over a broad range of intermediate inherent structure energy, bicontinuous phase separation prevails with interpenetrating stripes as signatures of spinodal decomposition. At low inherent structure energy, the structure is largely phase separated with one interface where as at high inherent structure energy we find nucleation type growth. Interestingly, at low temperature, the average inherent structure energy () exhibits a drop with temperature which signals the onset of crystallization in one of the phases while the other remains in the liquid state. The nonideal composition dependence of viscosity is anticorrelated with average inherent structure energy.