Improved Calculation of Vibrational Mode Lifetimes in Anharmonic Solids - Part I: Theory

We propose here a formal foundation for practical calculations of vibrational mode lifetimes in solids. The approach is based on a recursion method analysis of the Liouvillian. From this we derive the lifetime of a vibrational mode in terms of moments of the power spectrum of the Liouvillian as projected onto the relevant subspace of phase space. In practical terms, the moments are evaluated as ensemble averages of well-defined operators, meaning that the entire calculation is to be done with Monte Carlo. These insights should lead to significantly shorter calculations compared to current methods. A companion piece presents numerical results.Comment: 18 pages, 3 figure

Probability as a physical motive

Recent theoretical progress in nonequilibrium thermodynamics, linking the physical principle of Maximum Entropy Production ("MEP") to the information-theoretical "MaxEnt" principle of scientific inference, together with conjectures from theoretical physics that there may be no fundamental causal laws but only probabilities for physical processes, and from evolutionary theory that biological systems expand "the adjacent possible" as rapidly as possible, all lend credence to the proposition that probability should be recognized as a fundamental physical motive. It is further proposed that spatial order and temporal order are two aspects of the same thing, and that this is the essence of the second law of thermodynamics.Comment: Replaced at the request of the publisher. Minor corrections to references and to Equation 1 added

Structure of penetrable-rod fluids: Exact properties and comparison between Monte Carlo simulations and two analytic theories

Bounded potentials are good models to represent the effective two-body interaction in some colloidal systems, such as dilute solutions of polymer chains in good solvents. The simplest bounded potential is that of penetrable spheres, which takes a positive finite value if the two spheres are overlapped, being 0 otherwise. Even in the one-dimensional case, the penetrable-rod model is far from trivial, since interactions are not restricted to nearest neighbors and so its exact solution is not known. In this paper we first derive the exact correlation functions of penetrable-rod fluids to second order in density at any temperature, as well as in the high-temperature and zero-temperature limits at any density. Next, two simple analytic theories are constructed: a high-temperature approximation based on the exact asymptotic behavior in the limit $T\to\infty$ and a low-temperature approximation inspired by the exact result in the opposite limit $T\to 0$. Finally, we perform Monte Carlo simulations for a wide range of temperatures and densities to assess the validity of both theories. It is found that they complement each other quite well, exhibiting a good agreement with the simulation data within their respective domains of applicability and becoming practically equivalent on the borderline of those domains. A perspective on the extension of both approaches to the more realistic three-dimensional case is provided.Comment: 19 pages, 11 figures, 4 tables: v2: minor changes; published final versio

Influence of the Particles Creation on the Flat and Negative Curved FLRW Universes

We present a dynamical analysis of the (classical) spatially flat and negative curved Friedmann-Lameitre-Robertson-Walker (FLRW) universes evolving, (by assumption) close to the thermodynamic equilibrium, in presence of a particles creation process, described by means of a realiable phenomenological approach, based on the application to the comoving volume (i. e. spatial volume of unit comoving coordinates) of the theory for open thermodynamic systems. In particular we show how, since the particles creation phenomenon induces a negative pressure term, then the choice of a well-grounded ansatz for the time variation of the particles number, leads to a deep modification of the very early standard FLRW dynamics. More precisely for the considered FLRW models, we find (in addition to the limiting case of their standard behaviours) solutions corresponding to an early universe characterized respectively by an "eternal" inflationary-like birth and a spatial curvature dominated singularity. In both these cases the so-called horizon problem finds a natural solution.Comment: 14 pages, no figures, appeared in Class. Quantum Grav., 18, 193, 200

Two-chamber lattice model for thermodiffusion in polymer solutions

When a temperature gradient is applied to a polymer solution, the polymer typically migrates to the colder regions of the fluid as a result of thermal diffusion (Soret effect). However, in recent thermodiffusion experiments on poly(ethylene-oxide) (PEO) in a mixed ethanol/water solvent it is observed that for some solvent compositions the polymer migrates to the cold side, while for other compositions it migrates to the warm side. In order to understand this behavior, we have developed a two-chamber lattice model approach to investigate thermodiffusion in dilute polymer solutions. For a short polymer chain in an incompressible, one-component solvent we obtain exact results for the partitioning of the polymer between a warm and a cold chamber. In order to describe mixtures of PEO, ethanol, and water, we have extended this simple model to account for compressibility and hydrogen bonding between PEO and water molecules. For this complex system, we obtain approximate results for the composition in the warmer and cooler chambers that allow us to calculate Soret coefficients for given temperature, pressure, and solvent composition. The sign of the Soret coefficient is found to change from negative (polymer enriched in warmer region) to positive (polymer enriched in cooler region) as the water content of the solution is increased, in agreement with experimental data. We also investigate the temperature dependence of the Soret effect and find that a change in temperature can induce a change in the sign of the Soret coefficient. We note a close relationship between the solvent quality and the partitioning of the polymer between the two chambers, which may explain why negative Soret coefficients for polymers are so rarely observed.Comment: 12 pages, 8 figure

Tsallis statistics generalization of non-equilibrium work relations

We use third constraint formulation of Tsallis statistics and derive the $q$-statistics generalization of non-equilibrium work relations such as the Jarzynski equality and the Crooks fluctuation theorem which relate the free energy differences between two equilibrium states and the work distribution of the non-equilibrium processes.Comment: 5 page

Reactivity of a silica network of glass Molecular mechanism of the dissolution of a silica network in aqueous HF-HCI solutions

The molecular model of the dissolution mechanism of a silica network of glass in aqueous HF-HCl solutions is proposed. This model is based on two main assumptions: Firstly, the silicon atoms of the silica network are not saturated coordinatively and link with oxygen and fluorine atoms of the surface having a double-bond character. The dπ-pπ bonds are responsible for the change of polarity of the bonds Siδ+ - Oδ- and Siδ+ - Fδ- to Siδ- - Oδ+ and Siδ- - Fδ+. Secondly, there are two types of adsorption sites an a silica surface: the sites which act as acceptors of protons and the sites which act as donors of protons. The kinetic equations for the dissolution rate of a silica network of glass in aqueous HF-HCl solutions derived from the model are described. They assume a first-order dependence on HF2 - ions concentration in the solution. The concentration dependence on H+ and HF expressed by Langmuir's isotherms are described. The experimental results confirm the proposed model. It is shown that the increase in the dissolution rate of a silica network of glass in aqueous HF-HCl solutions is due to the increase in electronic density on the glass surface. HF molecules and HF2 - ions adsorbed on this surface were responsible for the increase in electronic density. The interactions of a silica network of glass with the HF-HCl solutions are highly autocatalytic as assumed in the model. Protons play a catalytic role both in the reaction of HF molecules and HF2 - ions with the surface while the increase of the kinetic reaction constant for the reaction of protons with the surface is due to the HF molecules. The double role of the protons in the solution process is explained

Inflationary Models Driven by Adiabatic Matter Creation

The flat inflationary dust universe with matter creation proposed by Prigogine and coworkers is generalized and its dynamical properties are reexamined. It is shown that the starting point of these models depends critically on a dimensionless parameter $\Sigma$, closely related to the matter creation rate $\psi$. For $\Sigma$ bigger or smaller than unity flat universes can emerge, respectively, either like a Big-Bang FRW singularity or as a Minkowski space-time at $t=-\infty$. The case $\Sigma=1$ corresponds to a de Sitter-type solution, a fixed point in the phase diagram of the system, supported by the matter creation process. The curvature effects have also been investigated. The inflating de Sitter is a universal attractor for all expanding solutions regardless of the initial conditions as well as of the curvature parameter.Comment: 25 pages, 2 figures(available from the authors), uses LATE

Exact Markovian kinetic equation for a quantum Brownian oscillator

We derive an exact Markovian kinetic equation for an oscillator linearly coupled to a heat bath, describing quantum Brownian motion. Our work is based on the subdynamics formulation developed by Prigogine and collaborators. The space of distribution functions is decomposed into independent subspaces that remain invariant under Liouville dynamics. For integrable systems in Poincar\'e's sense the invariant subspaces follow the dynamics of uncoupled, renormalized particles. In contrast for non-integrable systems, the invariant subspaces follow a dynamics with broken-time symmetry, involving generalized functions. This result indicates that irreversibility and stochasticity are exact properties of dynamics in generalized function spaces. We comment on the relation between our Markovian kinetic equation and the Hu-Paz-Zhang equation.Comment: A few typos in the published version are correcte