Thermal Conductivity of Supercooled Water

The heat capacity of supercooled water, measured down to -37 {\deg}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 hypothetical 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 as 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.Comment: References added, typos corrected. Extrapolation for viscosity improved; results essentially unchange

Crossover critical behavior in the three-dimensional Ising model

The character of critical behavior in physical systems depends on the range of interactions. In the limit of infinite range of the interactions, systems will exhibit mean-field critical behavior, i.e., critical behavior not affected by fluctuations of the order parameter. If the interaction range is finite, the critical behavior asymptotically close to the critical point is determined by fluctuations and the actual critical behavior depends on the particular universality class. A variety of systems, including fluids and anisotropic ferromagnets, belongs to the three-dimensional Ising universality class. Recent numerical studies of Ising models with different interaction ranges have revealed a spectacular crossover between the asymptotic fluctuation-induced critical behavior and mean-field-type critical behavior. In this work, we compare these numerical results with a crossover Landau model based on renormalization-group matching. For this purpose we consider an application of the crossover Landau model to the three-dimensional Ising model without fitting to any adjustable parameters. The crossover behavior of the critical susceptibility and of the order parameter is analyzed over a broad range (ten orders) of the scaled distance to the critical temperature. The dependence of the coupling constant on the interaction range, governing the crossover critical behavior, is discussedComment: 10 pages in two-column format including 9 figures and 1 table. Submitted to J. Stat. Phys. in honor of M. E. Fisher's 70th birthda

Boundary effects on the nonequilibrium structure factor of fluids below the Rayleigh-Benard instability

We consider a horizontal fluid layer between two rigid boundaries, maintained in a stationary thermal nonequilibrium state below the convective Rayleigh-Benard instability. We derive an explicit expression for the nonequilibrium structure factor in a first-order Galerkin approximation valid for negative and positive Rayleigh numbers R up to the critical Rayleigh number R(c) associated with the appearance of convection. The results obtained for rigid boundaries by the Galerkin-approximation method are compared with exact results previously derived for the case of free boundaries. The nonequilibrium structure factor exhibits a maximum as a function of the wave number q of the fluctuations. This maximum is associated with a crossover from a q(-4) dependence for larger q to a q(2) dependence for small q. This maximum is present at both negative and positive R, becomes pronounced at positive R and diverges as R approaches the critical value R(c)

Frame-invariant Fick diffusion matrices of multicomponent fluid mixtures

Extension of a description of mass diffusion in binary fluids based on Fick's law to multicomponent fluids requires introduction of diffusion matrices. A problem is that Fick diffusion matrices commonly adopted for multicomponent fluids depend on the velocity frame of reference. In this paper we show how one can define Fick diffusion matrices for multicomponent fluids that are frame invariant

Static and Dynamic Critical Behavior of a Symmetrical Binary Fluid: A Computer Simulation

A symmetrical binary, A+B Lennard-Jones mixture is studied by a combination of semi-grandcanonical Monte Carlo (SGMC) and Molecular Dynamics (MD) methods near a liquid-liquid critical temperature $T_c$. Choosing equal chemical potentials for the two species, the SGMC switches identities (${\rm A} \to {\rm B} \to {\rm A}$) to generate well-equilibrated configurations of the system on the coexistence curve for $T<T_c$ and at the critical concentration, $x_c=1/2$, for $T>T_c$. A finite-size scaling analysis of the concentration susceptibility above $T_c$ and of the order parameter below $T_c$ is performed, varying the number of particles from N=400 to 12800. The data are fully compatible with the expected critical exponents of the three-dimensional Ising universality class. The equilibrium configurations from the SGMC runs are used as initial states for microcanonical MD runs, from which transport coefficients are extracted. Self-diffusion coefficients are obtained from the Einstein relation, while the interdiffusion coefficient and the shear viscosity are estimated from Green-Kubo expressions. As expected, the self-diffusion constant does not display a detectable critical anomaly. With appropriate finite-size scaling analysis, we show that the simulation data for the shear viscosity and the mutual diffusion constant are quite consistent both with the theoretically predicted behavior, including the critical exponents and amplitudes, and with the most accurate experimental evidence.Comment: 35 pages, 13 figure