Microcanonical Entropy, Partitions of a Natural Number into Squares and the Bose-Einstein Gas in a Box.

From basic principles, we review some fundamentals of entropy calculations, some of which are implicit in the literature. We mainly deal with microcanonical ensembles to effectively compare the counting of states in continuous and discrete settings. When dealing with non-interacting elements, this effectively reduces the calculation of the microcanonical entropy to counting the number of certain partitions, or compositions of a number. This is true in the literal sense, when quantization is assumed, even in the classical limit. Thus, we build on a moderately dated, ingenuous mathematical work of Haselgrove and Temperley on counting the partitions of an arbitrarily large positive integer into a fixed (but still large) number of summands, and show that it allows us to exactly calculate the low energy/temperature entropy of a one-dimensional Bose-Einstein gas in a box. Next, aided by the asymptotic analysis of the number of compositions of an integer as the sum of three squares, we estimate the entropy of the three-dimensional problem. For each selection of the total energy, there is a very sharp optimal number of particles to realize that energy. Therefore, the entropy is 'large' and almost independent of the particles, when the particles exceed that number. This number scales as the energy to the power of ( 2 / 3 ) -rds in one dimension, and ( 3 / 5 ) -ths in three dimensions. In the one-dimensional case, the threshold approaches zero temperature in the thermodynamic limit, but it is finite for mesoscopic systems. Below that value, we studied the intermediate stage, before the number of particles becomes a strong limiting factor for entropy optimization. We apply the results of moments of partitions of Coons and Kirsten to calculate the relative fluctuations of the ground state and excited states occupation numbers. At much lower temperatures than threshold, they vanish in all dimensions. We briefly review some of the same results in the grand canonical ensemble to show to what extents they differ.

Density functional theory of nematic elasticity: softening from the polar order.

Recent experiments have evidenced some unconventional features in the elasticity of nematics, which cannot be explained by standard microscopic theories. Here, in the framework of a second-virial density functional theory, we have developed a general approach, relaxing the usual assumption that the angular distribution of particles with respect to their local director is unaffected by the deformation. We show that, for particles with polar symmetry, a new contribution to the splay and bend deformation free energy arises, associated with the onset of polar order. Calculations for conical and bent-shaped particles reveal dramatic softening of the splay and the bend mode, respectively, which eventually may lead to spontaneous deformation.

Thermal noise of mechanical oscillators in steady states with a heat flux.

We present an experimental investigation of the statistical properties of the position fluctuations of low-loss oscillators in nonequilibrium steady states. The oscillators are coupled to a heat bath, and a nonequilibrium steady state is produced by flowing a constant heat flux, setting a temperature difference across the oscillators. We investigated the distribution of the measurements of the square of the oscillator position and searched for signs of changes with respect to the equilibrium case. We found that, after normalization by the mean value, the second, third, and fourth standardized statistical moments are not modified by the underlying thermodynamic state. This differs from the behavior of the absolute, i.e., not normalized, second moment, which is strongly affected by temperature gradients and heat fluxes. We illustrate this with a numerical experiment in which we study via molecular dynamics the fluctuations of the length of a one-dimensional chain of identical particles interacting via anharmonic interparticle potentials, with the extremes thermostated at different temperatures: we use the variance of the length in correspondence to its first elastic mode of resonance to define an effective temperature which we observe to depart from the thermodynamic one in the nonequilibrium states. We investigate the effect of changing the interparticle potential and show that the qualitative behavior of the nonequilibrium excess is unchanged. Our numerical results are consistent with the chain length being Gaussian distributed in the nonequilibrium states. Our experimental investigation reveals that the position variance is the only, and crucially easily accessible, observable for distinguishing equilibrium from nonequilibrium steady states. The consequences of this fact for the design of interferometric gravitational wave detectors are discussed.

Elasticity of mechanical oscillators in nonequilibrium steady states: experimental, numerical, and theoretical results.

We study experimentally, numerically, and theoretically the elastic response of mechanical resonators along which the temperature is not uniform, as a consequence of the onset of steady-state thermal gradients. Two experimental setups and designs are employed, both using low-loss materials. In both cases, we monitor the resonance frequencies of specific modes of vibration, as they vary along with variations of temperatures and of temperature differences. In one case, we consider the first longitudinal mode of vibration of an aluminum alloy resonator; in the other case, we consider the antisymmetric torsion modes of a silicon resonator. By defining the average temperature as the volume-weighted mean of the temperatures of the respective elastic sections, we find out that the elastic response of an object depends solely on it, regardless of whether a thermal gradient exists and, up to 10% imbalance, regardless of its magnitude. The numerical model employs a chain of anharmonic oscillators, with first- and second-neighbor interactions and temperature profiles satisfying Fourier's Law to a good degree. Its analysis confirms, for the most part, the experimental findings and it is explained theoretically from a statistical mechanics perspective with a loose notion of local equilibrium.

Dynamically arrested states of matter.

We outline current developments in our understanding of dynamical arrest, that phenomenon in which many particles stop moving in a collective manner. However in addition to the question of true dynamical arrest itself, we emphasize the development of new tools that can describe relatively sharp changes in the way that ergodic systems may be explored. We discuss the concept of new order parameters (dynamically available volume), and indicate how they may be applied to understand dramatic slowing phenomena present in particle systems, and other arenas of soft and complex matter.

Geometry of dynamically available empty space is the key to near-arrest dynamics.

We study several examples of kinetically constrained lattice models using dynamically accessible volume as an order parameter. Thereby we identify two distinct regimes exhibiting dynamical slowing, with a sharp threshold between them. These regimes are identified both by a new response function in dynamically available volume, as well as directly in the dynamics. Results for the self-diffusion constant in terms of the connected hole density are presented, and some evidence is given for scaling in the limit of dynamical arrest.

Exact solution of a jamming transition: closed equations for a bootstrap percolation problem.

Jamming, or dynamical arrest, is a transition at which many particles stop moving in a collective manner. In nature it is brought about by, for example, increasing the packing density, changing the interactions between particles, or otherwise restricting the local motion of the elements of the system. The onset of collectivity occurs because, when one particle is blocked, it may lead to the blocking of a neighbor. That particle may then block one of its neighbors, these effects propagating across some typical domain of size named the dynamical correlation length. When this length diverges, the system becomes immobile. Even where it is finite but large the dynamics is dramatically slowed. Such phenomena lead to glasses, gels, and other very long-lived nonequilibrium solids. The bootstrap percolation models are the simplest examples describing these spatio-temporal correlations. We have been able to solve one such model in two dimensions exactly, exhibiting the precise evolution of the jamming correlations on approach to arrest. We believe that the nature of these correlations and the method we devise to solve the problem are quite general. Both should be of considerable help in further developing this field.

Simultaneous release of hydrophobic and cationic solutes from thin-film "plum-pudding" gels: a multifunctional platform for surface drug delivery?

The release of two compositionally different solutes from a composite gel composed of two different populations of microgel particles embedded in a single bulk gel matrix is described, showing the potential of the "plum-pudding gel" as a multifunctional platform for controlled surface release. One hydrophobic solute (pyrene) and one hydrophobic and charged solute (rhodamine 123) were chosen as the solutes to be released. Hydrophobic microgels composed of 50% N-isopropylacrylamide (NIPAM) and 50% N-tert-butylacrylamide (BAM) were loaded with pyrene, and anionic microgels composed of 30% acrylic acid (AAc), 20% NIPAM, and 50% BAM were loaded with rhodamine 123. The two solute-loaded microgel populations were incorporated into a single bulk gel network, from which the two solutes were released simultaneously and independently. Using this structural motif, solutes that are mutually incompatible can be incorporated into a single matrix with which they may also be incompatible. The electrostatically incorporated solute was released much more slowly than the hydrophobically attracted solute, indicating that the microgel composition can be tailored to the specific solute, and thus control its release rate. The choice of bulk matrix was also found to influence the release rate much more than expected, offering a further control element to the system.

Clarification of the bootstrap percolation paradox.

We study the onset of the bootstrap percolation transition as a model of generalized dynamical arrest. Our results apply to two dimensions, but there is no significant barrier to extending them to higher dimensionality. We develop a new importance-sampling procedure in simulation, based on rare events around "holes", that enables us to access bootstrap lengths beyond those previously studied. By framing a new theory in terms of paths or processes that lead to emptying of the lattice we are able to develop systematic corrections to the existing theory and compare them to simulations. Thereby, for the first time in the literature, it is possible to obtain credible comparisons between theory and simulation in the accessible density range.