In memoriam J. Robert Dorfman
An obituary of J.R. Dorfman. The focus is on his scientific career and on his many important publications.
cond-mat.stat-mech↗
arXiv subjects
J. V. Sengers
Publications and source records attributed to J. V. Sengers.
Nonequilibrium Casimir pressures in liquids under shear
In stationary nonequilibrium states coupling between hydrodynamic modes causes thermal fluctuations to become long ranged inducing nonequilibrium Casimir pressures. Here we consider nonequilibrium Casimir pressures induced in liquids by a velocity gradient. Specifically, we have obtained explicit expressions for the magnitude of the shear-induced pressure enhancements in a liquid layer between two horizontal plates that complete and correct results previously presented in the literature. In contrast to nonequilibrium Casimir pressures induced by a temperature or concentration gradient, we find that in shear nonequilibrium contributions from short-range fluctuations are no longer negligible. In addition, it is noted that currently available computer simulations of model fluids in shear observe effects from molecular correlations at nanoscales that have a different physical origin and do not probe shear-induced pressures resulting from coupling of long-wavelength hydrodynamic modes. Even more importantly, we find that in actual experimental conditions, shear-induced pressure enhancements are caused by viscous heating and not by thermal velocity fluctuations. Hence, isothermal computer simulations are irrelevant for the interpretation of experimental shear-induced pressure enhancements.
cond-mat.stat-mech↗
Shear-induced Casimir forces in liquid layers
In stationary nonequilibrium states a coupling between hydrodynamic modes causes thermal fluctuations to become long ranged inducing nonequilibrium Casimir forces or pressures. Here we consider nonequilibrium Casimir pressures induced in liquids by a velocity gradient. Specifically, we have obtained explicit expressions for the magnitude of the shear-induced pressure enhancement in a liquid layer between two horizontal plates that complete and correct results previously presented in the literature. In contrast to nonequiibrium Casimir pressures induced by a temperature gradient, kinetic theory shows that nonequilibrium contributions from short-range fluctuations are no longer negligible. In addition, it is noted that computer simulations of model fluids in shear observe effects from molecular correlations at nanoscales that have a different physical origin. The idea that such computer simulations probe shear-induced pressures resulting from coupling of long-wavelength hydrodynamic modes is erroneous.
cond-mat.stat-mech↗
Work probability distribution for a ferromagnet with long-ranged and short-ranged correlations
Work fluctuations and work probability distributions are fundamentally different in systems with short- ranged versus long-ranged correlations. Specifically, in systems with long-ranged correlations the work distribution is extraordinarily broad compared to systems with shortranged correlations. This difference profoundly affects the possible applicability of fluctuation theorems like the Jarzynski fluctuation theorem. The Heisenberg ferromagnet , well below its Curie temperature, is a system with long-ranged correlations in very low magnetic fields due to the presence of Goldstone modes. As the magnetic field is increased the correlations gradually become short-ranged. Hence, such a ferromagnet is an ideal system for elucidating the changes of the work probability distribution as one goes from a domain with long-ranged correlations to a domain with short-ranged correlations by tuning the magnetic field. A quantitative analysis of this crossover behaviour of the work probability distribution and the associated fluctuations is presented.
cond-mat.stat-mech↗
Contrasting work fluctuations and distributions in systems with short-range and long-range correlations
It is shown that the work fluctuations and work distribution functions are fundamentally different in systems with short-range versus long-range correlations. The two cases considered with long- range correlations are magnetic work fluctuations in an equilibrium isotropic ferromagnet, and work fluctuations in a non-equilibrium fluid with a temperature gradient. The long-range correlations in the former case are due to equilibrium Goldstone modes, while in the latter they are due to generic non-equilibrium effects. The magnetic case is of particular interest since an external magnetic field can be used to tune the system from one with long-range correlations, to one with only short- range correlations. It is shown that in systems with long-range correlations the work distribution is extraordinarily broad compared to systems with only short-range correlations. Surprisingly these results imply that fluctuations theorems such as the Jarzynski fluctuation theorem are more useful in systems with long-range correlations than in systems with short-range correlations.
cond-mat.stat-mech↗
Work, work fluctuations, and the work distribution in a thermal non-equilibrium steady state
Long-ranged correlations generically exist in non-equilibrium fluid systems. In the case of a non-equilibrium steady state caused by a temperature gradient the correlations are especially long-ranged and strong. The anomalous light scattering predicted to exist in these systems is well-confirmed by numerous experiments. Recently the Casimir force or pressure due to these fluctuations or correlations have been discussed in great detail. In this paper the notion of a Casimir work is introduced and a novel way to measure the non-equilibrium Casimir force is suggested. In particular, the non-equilibrium Casimir force is related to a non-equilibrium heat and not, as in equilibrium, to a volume derivative of an average energy. The non-equilibrium work fluctuations are determined and shown to be very anomalous compared to equilibrium work fluctuations. The non-equilibrium work distribution is also computed, and contrasted to work distributions in systems with short-range correlations. Again, there is a striking difference in the two cases. Formal theories of work and work distributions in non-equilibrium steady states are not explicit enough to illustrate any of these interesting features.
cond-mat.stat-mech↗
Nonequilibrium fluctuation-induced Casimir pressures in liquid mixtures
In this article we derive expressions for Casimir-like pressures induced by nonequilibrium concentration fluctuations in liquid mixtures. The results are then applied to liquid mixtures in which the concentration gradient results from a temperature gradient through the Soret effect. A comparison is made between the pressures induced by nonequilibrium concentration fluctuations in liquid mixtures and those induced by nonequilibrium temperature fluctuations in one-component fluids. Some suggestions for experimental verification procedures are also presented.
cond-mat.stat-mech↗
Physical origin of nonequilibrium fluctuation-induced forces in fluids
Long-range thermal fluctuations appear in fluids in nonequilibrium states leading to fluctuation-induced Casimir-like forces. Two distinct mechanisms have been identified for the origin of the long-range nonequilibrium fluctuations in fluids subjected to a temperature or concentration gradient. One is a coupling between the heat or mass-diffusion mode with a viscous mode in fluids subjected to a temperature or concentration gradient. Another one is the spatial inhomogeneity of thermal noise in the presence of a gradient. We show that in fluids fluctuation-induced forces arising from mode coupling are several orders of magnitude larger than those from inhomogeneous noise.
cond-mat.stat-mech↗
Why Non-equilibrium is Different
The 1970 paper, "Decay of the Velocity Correlation Function" [Phys. Rev. A1, 18 (1970), see also Phys. Rev. Lett. 18, 988 (1967)] by Berni Alder and Tom Wainwright, demonstrated, by means of computer simulations, that the velocity autocorrelation function for a particle in a gas of hard disks decays algebraically in time as $t^{-1},$ and as $t^{-3/2}$ for a gas of hard spheres. These decays appear in non-equilibrium fluids and have no counterpart in fluids in thermodynamic equilibrium. The work of Alder and Wainwright stimulated theorists to find explanations for these "long time tails" using kinetic theory or a mesoscopic mode-coupling theory. This paper has had a profound influence on our understanding of the non-equilibrium properties of fluid systems. Here we discuss the kinetic origins of the long time tails, the microscopic foundations of mode-coupling theory, and the implications of these results for the physics of fluids. We also mention applications of the long time tails and mode-coupling theory to other, seemingly unrelated, fields of physics. We are honored to dedicate this short review to Berni Alder on the occasion of his 90th birthday!
cond-mat.stat-mech↗
Non-equilibrium concentration fluctuations in binary liquids with realistic boundary conditions
Because of the spatially long-ranged nature of spontaneous fluctuations in thermal non-equilibrium systems, they are affected by boundary conditions for the fluctuating hydrodynamic variables. In this paper we consider a liquid mixture between two rigid and impervious plates with a stationary concentration gradient resulting from a temperature gradient through the Soret effect. For liquid mixtures with a large Lewis number, we are able to obtain explicit analytical expressions for the intensity of the non-equilibrium concentration fluctuations as a function of the frequency $ω$ and the wave number $q$ of the fluctuations. In addition we elucidate the spatial dependence of the intensity of the non-equilibrium fluctuations responsible for a non-equilibrium Casimir effect.
cond-mat.stat-mech↗
Non-equilibrium Casimir-like Forces in Liquid Mixtures
In this Letter we consider a liquid mixture confined between two thermally conducting walls subjected to a stationary temperature gradient. While in a one-component liquid non-equilibrium fluctuation forces appear inside the liquid layer only, non-equilibrium fluctuations in a mixture induce a Casimir-like force on the walls. The physical reason is that the temperature gradient induces large concentration fluctuations through the Soret effect. Unlike temperature fluctuations, non-equilibrium concentration fluctuations are also present near a perfectly thermally conducting wall. The magnitude of the fluctuation-induced Casimir force is proportional to the square of the Soret coefficient and is related to the concentration dependence of the heat and volume of mixing.
cond-mat.stat-mech↗
Kinetic Theory of Drag on Objects in Nearly Free Molecular Flow
Using an analogy between the density expansion of the transport coefficients of moderately dense gases and the inverse-Knudsen-number expansion of the drag on objects in nearly free molecular flows, we formulate the collision integrals that determine the first correction term to the free-molecular drag limit. We then show how the procedure can be applied to calculate the drag coefficients of an oriented disc and a sphere as a function of the speed ratio.
cond-mat.stat-mech↗
Minimum in the thermal conductivity of supercooled water: a computer simulation study
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.
cond-mat.stat-mech↗
Fluctuation-induced pressures in fluids in thermal nonequilibrium steady states
Correlations in fluids in nonequilibrium steady states are long ranged. Hence, finite-size effects have important consequences in the nonequilibrium thermodynamics of fluids. One consequence is that nonequilibrium temperature fluctuations induce nonequilibrium Casimir-like pressures proportional to the square of the temperature gradient. Hence, fluctuations cause a breakdown of the concept of local thermal equilibrium. Furthermore, transport coefficients become dependent on boundary conditions and on gravity. Thus nonequilibrium fluctuations affect some traditional concepts in nonequilibrium thermodynamics.
cond-mat.stat-mech↗
Giant Casimir effect in fluids in non-equilibrium steady states
In this letter we consider the fluctuation induced force exerted between two plates separated by a distance $L$ in a fluid with a temperature gradient. We predict that, for a range of distances $L$, this non-equilibrium force is anomalously large compared to other Casimir forces. The physical reason is that correlations in a non-equilibrium fluid are generally of longer range than other correlations, even than those near an equilibrium critical point. This giant Casimir force is related to a divergent Burnett coefficient that characterizes an Onsager cross effect between the pressure and the temperature gradient. The predicted Casimir force should be detectable with currently available experimental techniques.
cond-mat.stat-mech↗
Thermodynamics of supercooled water
We review the available experimental information on the thermodynamic properties of supercooled ordinary and heavy water and demonstrate the possibility of modeling these thermodynamic properties on a theoretical basis. We show that by assuming the existence of a liquid-liquid critical point in supercooled water, the theory of critical phenomena can give an accurate account of the experimental thermodynamic-property data up to a pressure of 150 MPa. In addition, we show that a phenomenological extension of the theoretical model can account for all currently available experimental data in the supercooled region, up to 400 MPa. The stability limit of the liquid state and possible coupling between crystallization and liquid-liquid separation are discussed. It is concluded that critical-point thermodynamics describes the available thermodynamic data for supercooled water within experimental accuracy, thus establishing a benchmark for further developments in this area.
physics.chem-ph↗
Probing structural relaxation in complex fluids by critical fluctuations
Complex fluids, such as polymer solutions and blends, colloids and gels, are of growing interest in fundamental and applied soft-condensed-matter science. A common feature of all such systems is the presence of a mesoscopic structural length scale intermediate between atomic and macroscopic scales. This mesoscopic structure of complex fluids is often fragile and sensitive to external perturbations. Complex fluids are frequently viscoelastic (showing a combination of viscous and elastic behaviour) with their dynamic response depending on the time and length scales. Recently, non-invasive methods to infer the rheological response of complex fluids have gained popularity through the technique of microrheology, where the diffusion of probe spheres in a viscoelastic fluid is monitored with the aid of light scattering or microscopy. Here we propose an alternative to traditional microrheology that does not require doping of probe particles in the fluid (which can sometimes drastically alter the molecular environment). Instead, our proposed method makes use of the phenomenon of "avoided crossing" between modes associated with the structural relaxation and critical fluctuations that are spontaneously generated in the system.
cond-mat.soft↗
Scaling of demixing curves and crossover from critical to tricritical behavior in polymer solutions
In this paper we show that the virial expansion up to third order for the osmotic pressure of a dilute polymer solution, including first-order perturbative corrections to the virial coefficients, allows for a scaling description of phase-separation data for polymer solutions in reduced variables. This scaling description provides a method to estimate the Theta-temperature, where demixing occurs in the limit of vanishing polymer volume fraction $ϕ$ and infinite chain-length $N$, without explicit assumptions concerning the chain-length dependence of the critical parameters $T_c$ and $ϕ_c$. The scaling incorporates three limiting regimes: the Ising limit asymptotically close to the critical point of phase separation, the pure solvent limit and, the tricritical limit for the polymer-rich phase asymptotically close to the Theta point. We incorporate the effects of critical and tricritical fluctuations on the coexistence curve scaling by using renormalization-group methods. We present a detailed comparison with experimental and simulation data for coexistence curves and compare our estimates for the Theta-temperatures of several systems with those obtained from different extrapolation schemes.
cond-mat.soft↗