Statistical mechanical theory for steady state systems. VII. Nonlinear theory

The second entropy theory for nonequilibrium thermodynamics is extended to the nonlinear regime and to systems of mixed parity (even and odd functions of molecular velocities). The steady state phase space probability density is given for systems of mixed parity. The nonlinear transport matrix is obtained and it is shown to yield the analog of the linear Onsager-Casimir reciprocal relations. Its asymmetric part contributes to the flux and to the production of second entropy. The nonlinear transport matrix is not simply expressible as a Green-Kubo fluctuation equilibrium time correlation function. However, here the first nonlinear correction to the transport coefficient is given explicitly as a type of the Green-Kubo equilibrium time correlation function. The theory is illustrated by application to chemical kinetics.     

Statistical mechanical theory for steady state systems. V. Nonequilibrium probability density

The phase space probability density for steady heat flow is given. This generalizes the Boltzmann distribution to a nonequilibrium system. The expression includes the nonequilibrium partition function, which is a generating function for statistical averages and which can be related to a nonequilibrium free energy. The probability density is shown to give the Green-Kubo formula in the linear regime. A Monte Carlo algorithm is developed based upon a Metropolis sampling of the probability distribution using an umbrella weight. The nonequilibrium simulation scheme is shown to be much more efficient for the thermal conductivity of a Lennard-Jones fluid than the Green-Kubo equilibrium fluctuation method. The theory for heat flow is generalized to give the generic nonequilibrium probability densities for hydrodynamic transport, for time-dependent mechanical work, and for nonequilibrium quantum statistical mechanics.     

Statistical mechanical theory for steady state systems. II. Reciprocal relations and the second entropy

The concept of second entropy is introduced for the dynamic transitions between macrostates. It is used to develop a theory for fluctuations in velocity, and is exemplified by deriving Onsager reciprocal relations for Brownian motion. The cases of free, driven, and pinned Brownian particles are treated in turn, and Stokes' law is derived. The second entropy analysis is applied to the general case of thermodynamic fluctuations, and the Onsager reciprocal relations for these are derived using the method. The Green-Kubo formulas for the transport coefficients emerge from the analysis, as do Langevin dynamics.     

Statistical mechanical theory for steady state systems. IV. Transition probability and simulation algorithm demonstrated for heat flow

Two microscopic transition theorems are given for the probability of nonequilibrium work performed on a subsystem of a thermal reservoir along the trajectory in phase space of the subsystem. The resultant transition probability is applied to the case of heat flow down an applied temperature gradient. A combined molecular dynamics and Monte Carlo algorithm is given for such a nonequilibrium steady state. Results obtained for the thermal conductivity are in good agreement with previous Green-Kubo and nonequilibrium molecular dynamics results.     

Statistical mechanical theory for steady state systems. VIII. General theory for a Brownian particle driven by a time- and space-varying force

A Brownian particle subject to a time- and space-varying force is studied with the second entropy theory for nonequilibrium statistical mechanics. A fluctuation expression is obtained for the second entropy of the path, and this is maximized to obtain the most likely path of the particle. Two approaches are used, one based on the velocity correlation function and one based on the position correlation function. The approaches are a perturbation about the free particle result and are exact for weak external forces. They provide a particularly simple way of including memory effects in time-varying driven diffusion. The theories are tested against computer simulation data for a Brownian particle trapped in an oscillating parabolic well. They accurately predict the phase lag and amplitude as a function of drive frequency, and they account quantitatively for the memory effects that are important at high frequencies and that are missing in the simplest Langevin equation.     

Statistical mechanical theory for the structure of steady state systems: application to a Lennard-Jones fluid with applied temperature gradient

The constrained entropy and probability distribution are given for the structure that develops in response to an applied thermodynamic gradient, as occurs in driven steady state systems. The theory is linear but is applicable to gradients with arbitrary spatial variation. The phase space probability distribution is also given, and it is surprisingly simple with a straightforward physical interpretation. With it, all of the known methods of equilibrium statistical mechanics for inhomogeneous systems may now be applied to determining the structure of nonequilibrium steady state systems. The theory is illustrated by performing Monte Carlo simulations on a Lennard-Jones fluid with externally imposed temperature and chemical potential gradients. The induced energy and density moments are obtained, as well as the moment susceptibilities that give the rate of change of these with imposed gradient and which also give the fluctuations in the moments. It is shown that these moment susceptibilities can be written in terms of bulk susceptibilities and also that the Soret coefficient can be expressed in terms of them.     

Statistical mechanical theory for steady-state systems. III. Heat flow in a Lennard-Jones fluid

A statistical mechanical theory for heat flow is developed based upon the second entropy for dynamical transitions between energy moment macrostates. The thermal conductivity, as obtained from a Green-Kubo integral of a time correlation function, is derived as an approximation from these more fundamental theories, and its short-time dependence is explored. A new expression for the thermal conductivity is derived and shown to converge to its asymptotic value faster than the traditional Green-Kubo expression. An ansatz for the steady-state probability distribution for heat flow down an imposed thermal gradient is tested with simulations of a Lennard-Jones fluid. It is found to be accurate in the high-density regime at not too short times, but not more generally. The probability distribution is implemented in Monte Carlo simulations, and a method for extracting the thermal conductivity is given.     

Statistical mechanical theory of liquid entropy

The multiparticle correlation expansion for the entropy of a classical monatomic liquid is presented. This entropy expresses the physical picture in which there is no free particle motion, but, rather, each atom moves within a cage formed by its neighbors. The liquid expansion, including only pair correlations, gives an excellent account of the experimental entropy of most liquid metals, of liquid argon, and of the hard-sphere liquid. The pair correlation entropy is well approximated by a universal function of temperature. Higher-order correlation entropy, due to n-particle irreducible correlations for n ≥ 3, is significant in only a few liquid metals, and its occurrence suggests the presence of n-body forces. When the liquid theory is applied to the study of melting, we discover the important classification of normal and anomalous melting, according to whether there is not or is a significant change in the electronic structure upon melting, and we discover the universal disordering entropy for melting of a monatomic crystal. Interesting directions for future research are extension to include orientational correlations of molecules, theoretical calculation of the entropy of water, application to the entropy of the amorphous state, and correlational entropy of compressed argon. We clarify the relation among different entropy expansions in the recent literature. © 1994 John Wiley & Sons, Inc.     

Statistical mechanical theory of local compositions

The concept of local composition has received much attention during the past few years, much of which has been devoted to justifying the empirical model proposed by Wilson in 1964. In this report the concept of local composition is defined on statiscal mechanical grounds and expressions relating these compositions to thermodynamic properties of equilibrium fluid mixtures are derived. In particular, different local composition approximations are presented and new approximations based on molecular theories of mixtures are derived. Sets of mixing rules consistent with these different local composition approximations result, some of which are density and temperature dependent. Also, relations for partial molar properties in terms of local compositions are derived from the Kirkwood-Buff solution theory. Finally the radius of the sphere of influence of local compositions is formulated on statistical mechanical grounds.     

Variational transition state theory without the minimum-energy path

In this paper we propose a method for carrying out variational transition state theory calculations without first obtaining a converged minimum-energy path (MEP). We illustrate the method in two ways, first of all by employing an unconverged MEP and secondly by using a dynamically optimized distinguished reaction path. Preliminary tests of the algorithm for the reactions OH+H₂→H₂O+H and C₂H₅→C₂H₄+H are very encouraging. Received: 22 January 1997 / Accepted: 11 March 1997     

Statistical mechanical theory for discotic liquid crystals Discotic nematic-isotropic transition properties

A statistical mechanical theory is applied to study the equilibrium properties of discotic nematic liquid crystals. We report the calculation of thermodynamic properties for a model system composed of molecules interacting through angle-dependent pair potentials which can be broken up into rapidly varying short-ranged repulsions and weak long-range attractions. The repulsive interaction is represented by a repulsion between hard oblate ellipsoids of revolution and is a short-range, rapidly-varying, potential. The influence of attractive potentials, represented by dispersion and quadrupole interactions on a variety of thermodynamic properties is analysed. It is found that the thermodynamic properties for the discotic nematic-isotropic transition are highly sensitive to the form of effective one-body orientational perturbation potential. The discontinuity in the transition properties is more pronounced in the case of quadrupole interaction than for anisotropic dispersion interaction. A remarkable symmetry in the transition properties between prolate ellipsoids (ordinary nematic) and oblate ellipsoids (discotic nematic) is observed.     

Phospha-S-triazines. VI. Polymeric systems

Two types of polymeric phospha-s-triazines were synthesized: poly(perfluoroalkylethermonophospha-s-triazines) and monocyclic mono- and diphospha-s-triazines substituted on the carbon ring atoms by poly- (perfluoroalkylether) chains. The polymeric system consisting of the monophospha-s-triazine rings joined by perfluoroalkylether chains were found to have lower thermal oxidative stability than that shown by the corresponding dumbbell compounds. The monocyclic materials substituted by poly(perfluoroalkylether) chains possessed good thermal and oxidative stability, in addition to exhibiting anticorrosive and antioxidative properties.     

Variational principles for describing chemical reactions. Reactivity indices based on the external potential.

In a recent paper [J. Am. Chem. Soc. 2000, 122, 2010], the authors explored variational principles that help one understand chemical reactivity on the basis of the changes in electron density associated with a chemical reaction. Here, similar methods are used to explore the effect changing the external potential has on chemical reactivity. Four new indices are defined: (1) a potential energy surface that results from the second-order truncation of the Taylor series in the external potential about some reference, Upsilon(R(1),R(2),.,R(M)()); (2) the stabilization energy for the equilibrium nuclear geometry (relative to some reference), Xi; (3) the flexibility, or "lability", of the molecule at equilibrium, Lambda; and (4) the proton hardness, Pi, which performs a role in the theory of Br?nsted-Lowry acids and bases that is similar to the role of the chemical hardness in the theory of Lewis acids and bases. Applications considered include the orientation of a molecule in an external electric field, molecular association reactions, and reactions between Br?nsted-Lowry acids and bases.     

Statistical theory of turbulent mass transfer in electrochemical systems

The paper presents an overview of the statistical theory of turbulent mass transfer in electrochemical systems and some new results which generalize the previously obtained relations for the flows of complex geometry. The developed theory does not use traditional semi-empirical hypotheses and analogies, but directly addresses to the solving of the critical for turbulent transfer the closure problem. The mathematical procedure for solving of the closure problem makes use of new equations for the correlations between concentration and velocity fluctuations in different space points and at different time moments; the dumping of turbulent pulsations in the viscous sublayer allows to neglect high order moments and obtain a closed equation for the turbulent mass flux. In general, the relation between the turbulent mass flux and the mean concentration gradient is non-local. Using available experimental information, the non-local equation for the turbulent mass flux is reduced to the traditional local one and the functional form of the turbulent diffusion coefficient is obtained. It is demonstrated that Reynolds analogy cannot been used for the prediction of the turbulent diffusivity. Applications of the developed theory to chemical engineering and to electrochemical flow diagnostics (prediction of flow characteristics using limiting diffusion current measurements) are discussed.     

Variational principles for E3

New variational principles are given for E₃ in RS perturbation theory, also a unified derivation of several other principles. An example with a unknown π₀ is treated.     

Communication: transition state theory for dissipative systems without a dividing surface

Transition state theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when the reactive system is coupled to an environment. The calculations made in this way then overestimate the reaction rate and the results depend critically on the choice of the dividing surface. In this Communication, we study the phase space of a stochastically driven system close to an energetic barrier in order to identify the geometric structure unambiguously determining the reactive trajectories, which is then incorporated in a simple rate formula for reactions in condensed phase that is both independent of the dividing surface and exact.     

The isokinetic relationship. VI. Equilibrium systems

The isoequilibrium relationship (IER), i.e. the occurrence of a common point of intersection of the van 't Hoff plots of a homologous reaction series, is investigated on the basis of a master equation theory describing forward and reverse reaction rates. The relation between the isoequilibrium temperature and the isokinetic temperatures of forward and reverse reactions is deduced theoretically and compared with experimental results.