Small and Simple Systems That Favor the Arrow of Time.

The 2nd law of thermodynamics yields an irreversible increase in entropy until thermal equilibrium is achieved. This irreversible increase is often assumed to require large and complex systems to emerge from the reversible microscopic laws of physics. We test this assumption using simulations and theory of a 1D ring of N Ising spins coupled to an explicit heat bath of N Einstein oscillators. The simplicity of this system allows the exact entropy to be calculated for the spins and the heat bath for any N, with dynamics that is readily altered from reversible to irreversible. We find thermal-equilibrium behavior in the thermodynamic limit, and in systems as small as N=2, but both results require microscopic dynamics that is intrinsically irreversible.

1/ f noise from the laws of thermodynamics for finite-size fluctuations.

Computer simulations of the Ising model exhibit white noise if thermal fluctuations are governed by Boltzmann's factor alone; whereas we find that the same model exhibits 1/f noise if Boltzmann's factor is extended to include local alignment entropy to all orders. We show that this nonlinear correction maintains maximum entropy during equilibrium fluctuations. Indeed, as with the usual way to resolve Gibbs' paradox that avoids entropy reduction during reversible processes, the correction yields the statistics of indistinguishable particles. The correction also ensures conservation of energy if an instantaneous contribution from local entropy is included. Thus, a common mechanism for 1/f noise comes from assuming that finite-size fluctuations strictly obey the laws of thermodynamics, even in small parts of a large system. Empirical evidence for the model comes from its ability to match the measured temperature dependence of the spectral-density exponents in several metals and to show non-Gaussian fluctuations characteristic of nanoscale systems.

Modified Bose-Einstein and Fermi-Dirac statistics if excitations are localized on an intermediate length scale: applications to non-Debye specific heat.

Disordered systems show deviations from the standard Debye theory of specific heat at low temperatures. These deviations are often attributed to two-level systems of uncertain origin. We find that a source of excess specific heat comes from correlations between quanta of energy if excitations are localized on an intermediate length scale. We use simulations of a simplified Creutz model for a system of Ising-like spins coupled to a thermal bath of Einstein-like oscillators. One feature of this model is that energy is quantized in both the system and its bath, ensuring conservation of energy at every step. Another feature is that the exact entropies of both the system and its bath are known at every step, so that their temperatures can be determined independently. We find that there is a mismatch in canonical temperature between the system and its bath. In addition to the usual finite-size effects in the Bose-Einstein and Fermi-Dirac distributions, if excitations in the heat bath are localized on an intermediate length scale, this mismatch is independent of system size up to at least 10(6) particles. We use a model for correlations between quanta of energy to adjust the statistical distributions and yield a thermodynamically consistent temperature. The model includes a chemical potential for units of energy, as is often used for other types of particles that are quantized and conserved. Experimental evidence for this model comes from its ability to characterize the excess specific heat of imperfect crystals at low temperatures.

A free-energy landscape picture and Landau theory for the dynamics of disordered materials.

Landau's theory of phase transitions [Nature (London) 138, 840 (1936); Statistical Physics (Pergamon, London, 1959)] is adapted to treat independently relaxing regions in complex systems using nanothermodynamics. The order parameter we use governs the thermal fluctuations, not a specific static structure. We find that the entropy term dominates the thermal behavior, as is reasonable for disordered systems. Consequently, the thermal equilibrium occurs at the internal-energy maximum, so that the potential-energy minima have negligible influence on the dynamics. The dynamics involves normal thermal fluctuations about the free-energy minimum, with a time scale that is governed by the curvature of the internal-energy maximum. The temperature dependence of the fluctuations yields Vogel-Tamman-Fulcher-type [Phys. Z. 22, 645 (1921); J. Am. Ceram. Soc. 8, 339 (1925); Z. Anorg. Allg. Chem. 156, 245 (1926)] relaxation rates and approximate time-temperature superposition, consistent with the Williams-Landell-Ferry [J. Am. Chem. Soc. 77, 3701 (1955)] procedure for analyzing the dynamics of complex fluids, while the size dependence of the fluctuations provides an explanation for the distribution of relaxation times and heterogeneity that are found in glass-forming liquids, thus providing a unified picture for several features in the dynamics of disordered materials.