Fragilities of Liquids Predicted from the Random First Order Transition Theory of Glasses

A microscopically motivated theory of glassy dynamics based on an underlying random first order transition is developed to explain the magnitude of free energy barriers for glassy relaxation. A variety of empirical correlations embodied in the concept of liquid "fragility" are shown to be quantitatively explained by such a model. The near universality of a Lindemann ratio characterizing the maximal amplitude of thermal vibrations within an amorphous minimum explains the variation of fragility with a liquid's configurational heat capacity density. Furthermore the numerical prefactor of this correlation is well approximated by the microscopic calculation. The size of heterogeneous reconfiguring regions in a viscous liquid is inferred and the correlation of nonexponentiality of relaxation with fragility is qualitatively explained. Thus the wide variety of kinetic behavior in liquids of quite disparate chemical nature reflects quantitative rather than qualitative differences in their energy landscapes.Comment: 10 pages including 4 eps figure

Onsager's missing steps retraced

Onsager's paper on phase transition and phase coexistence in anisotropic colloidal systems is a landmark in the theory of lyotropic liquid crystals. However, an uncompromising scrutiny of Onsager's original derivation reveals that it would be rigorously valid only for ludicrous values of the system's number density (of the order of the reciprocal of the number of particles) Based on Penrose's tree identity and an appropriate variant of the mean-field approach for purely repulsive, hard-core interactions, our theory shows that Onsager's theory is indeed valid for a reasonable range of densities

Contributions of Repulsive and Attractive Interactions to Nematic Order

Both repulsive and attractive molecular interactions can be used to explain the onset of nematic order. The object of this paper is to combine these two nematogenic molecular interactions in a unified theory. This attempt is not unprecedented; what is perhaps new is the focus on the understanding of nematics in the high density limit. There, the orientational probability distribution is shown to exhibit a unique feature: it has compact support on configuration space. As attractive interactions are turned on, the behavior changes, and at a critical attractive interaction strength, thermotropic behavior of the Maier-Saupe type is attained.Comment: 14 pages, 4 figure

On the hydrodynamics of swimming enzymes

Several recent experiments suggest that rather generally the diffusion of enzymes may be augmented through their activity. We demonstrate that such swimming motility can emerge from the interplay between the enzyme energy landscape and the hydrodynamic coupling of the enzyme to its environment. Swimming thus occurs during the transit time of a transient allosteric change. We estimate the velocity during the transition. The analysis of such a swimming motion suggests the final stroke size is limited by the hydrodynamic size of the enzyme. This limit is quite a bit smaller than the values that can be inferred from the recent experiments. We also show that one proposed explanation of the experiments based on reaction heat effects can be ruled out using an extended hydrodynamic analysis. These results lead us to propose an alternate explanation of the fluorescence correlation measurements

Density functional theory for dense nematics with steric interactions

The celebrated work of Onsager on hard particle systems, based on the truncated second order virial expansion, is valid at relatively low volume fractions for large aspect ratio particles. While it predicts the isotropic-nematic phase transition, it fails to provide a realistic equation of state in that the pressure remains finite for arbitrarily high densities. In this work, we derive a mean field density functional form of the Helmholtz free energy for nematics with hard core repulsion. In addition to predicting the isotropic-nematic transition, the model provides a more realistic equation of state. The energy landscape is much richer, and the orientational probability distribution function in the nematic phase possesses a unique feature: it vanishes on a nonzero measure set in orientational space

A confined rod: mean field theory for hard rod-like particles

In this paper, we model the configurations of a system of hard rods by viewing each rod in a cell formed by its neighbors. By minimizing the free energy in the model and performing molecular dynamics, where, in both cases, the shape of the cell is a free parameter, we obtain the equilibrium orientational order parameter, free energy and pressure of the system. Our model enables the calculation of anisotropic stresses exerted on the walls of the cell due to shape change of the rod in photoisomerization. These results are a key step towards understanding molecular shape change effects in photomechanical systems under illumination.Comment: 15 pages, 8 figure

Leaky cell model of hard spheres

We study packings of hard spheres on lattices. The partition function, and therefore the pressure, may be written solely in terms of the accessible free volume, i.e., the volume of space that a sphere can explore without touching another sphere. We compute these free volumes using a leaky cell model, in which the accessible space accounts for the possibility that spheres may escape from the local cage of lattice neighbors. We describe how elementary geometry may be used to calculate the free volume exactly for this leaky cell model in two- and three-dimensional lattice packings and compare the results to the well-known Carnahan–Starling and Percus–Yevick liquid models. We provide formulas for the free volumes of various lattices and use the common tangent construction to identify several phase transitions between them in the leaky cell regime, indicating the possibility of coexistence in crystalline materials

Leaky Cell Model of Hard Spheres

We study packings of hard spheres on lattices. The partition function, and therefore the pressure, may be written solely in terms of the accessible free volume, i.e., the volume of space that a sphere can explore without touching another sphere. We compute these free volumes using a leaky cell model, in which the accessible space accounts for the possibility that spheres may escape from the local cage of lattice neighbors. We describe how elementary geometry may be used to calculate the free volume exactly for this leaky cell model in two- and three-dimensional lattice packings and compare the results to the well-known Carnahan–Starling and Percus–Yevick liquid models. We provide formulas for the free volumes of various lattices and use the common tangent construction to identify several phase transitions between them in the leaky cell regime, indicating the possibility of coexistence in crystalline materials