Paško Županović

The Maximum Entropy Production Principle and Linear Irreversible Processes

It is shown that Onsager’s principle of the least dissipation of energy is equivalent to the maximum entropy production principle. It is known that solutions of the linearized Boltzmann equation make extrema of entropy production. It is argued, in the case of stationary processes, that this extremum is a maximum rather than a minimum.

Enzyme kinetics and the maximum entropy production principle.

A general proof is derived that entropy production can be maximized with respect to rate constants in any enzymatic transition. This result is used to test the assumption that biological evolution of enzyme is accompanied with an increase of entropy production in its internal transitions and that such increase can serve to quantify the progress of enzyme evolution. The state of maximum entropy production would correspond to fully evolved enzyme. As an example the internal transition ES↔EP in a generalized reversible Michaelis-Menten three state scheme is analyzed. A good agreement is found among experimentally determined values of the forward rate constant in internal transitions ES→EP for three types of β-Lactamase enzymes and their optimal values predicted by the maximum entropy production principle, which agrees with earlier observations that β-Lactamase enzymes are nearly fully evolved. The optimization of rate constants as the consequence of basic physical principle, which is the subject of this paper, is a completely different concept from a) net metabolic flux maximization or b) entropy production minimization (in the static head state), both also proposed to be tightly connected to biological evolution.

On the Problem of Formulating Principles in Nonequilibrium Thermodynamics

In this work, we consider the choice of a system suitable for the formulation of principles in nonequilibrium thermodynamics. It is argued that an isolated system is a much better candidate than a system in contact with a bath. In other words, relaxation processes rather than stationary processes are more appropriate for the formulation of principles in nonequilibrium thermodynamics. Arguing that slow varying relaxation can be described with quasi-stationary process, it is shown for two special cases, linear nonequilibrium thermodynamics and linearized Boltzmann equation, that solutions of these problems are in accordance with the maximum entropy production principle.

Spectral properties of quasi-one-dimensional conductors with a finite transverse band dispersion

We determine the one-particle spectral function and the corresponding derived quantities for the conducting chain lattice with finite inter-chain hopping and three-dimensional long-range Coulomb electron–electron interaction. The standard G0W0 approximation is used. It is shown that, due to the optical character of the anisotropic plasmon dispersion caused by the finite , a low energy quasi-particle δ-peak appears in the spectral function in addition to the hump present at energies of the order of the plasmon energy. Particular attention is devoted to the continuous crossover from the non-Fermi liquid regime to the Fermi liquid regime with increasing . It is shown that the spectral weight of the hump transfers to the quasi-particle as the optical gap in the plasmon dispersion increases together with , with the quasi-particle residuum Z behaving like in the limit . Our approach is appropriate for the wide range of energy scales given by the plasmon energy and the width of the conduction band, and is complementary to the Luttinger liquid techniques that are limited to the low energy regime close to the Fermi surface.

Maximum Entropy Production and Maximum Shannon Entropy as Germane Principles for the Evolution of Enzyme Kinetics

There have been many attempts to use optimization approaches to study the biological evolution of enzyme kinetics. Our basic assumption here is that the biological evolution of catalytic cycle fluxes between enzyme internal functional states is accompanied by increased entropy production of the fluxes and increased Shannon information entropy of the states. We use simplified models of enzyme catalytic cycles and bioenergetically important free-energy transduction cycles to examine the extent to which this assumption agrees with experimental data. We also discuss the relevance of Prigogine’s minimal entropy production theorem to biological evolution.

Relaxation Processes and the Maximum Entropy Production Principle

Spontaneous transitions of an isolated system from one macroscopic state to another (relaxation processes) are accompanied by a change of entropy. Following Jaynes’ MaxEnt formalism, it is shown that practically all the possible microscopic developments of a system, within a fixed time interval, are accompanied by the maximum possible entropy change. In other words relaxation processes are accompanied by maximum entropy production.

Macroscopic Time Evolution and MaxEnt Inference for Closed Systems with Hamiltonian Dynamics

MaxEnt inference algorithm and information theory are relevant for the time evolution of macroscopic systems considered as problem of incomplete information. Two different MaxEnt approaches are introduced in this work, both applied to prediction of time evolution for closed Hamiltonian systems. The first one is based on Liouville equation for the conditional probability distribution, introduced as a strict microscopic constraint on time evolution in phase space. The conditional probability distribution is defined for the set of microstates associated with the set of phase space paths determined by solutions of Hamilton’s equations. The MaxEnt inference algorithm with Shannon’s concept of the conditional information entropy is then applied to prediction, consistently with this strict microscopic constraint on time evolution in phase space. The second approach is based on the same concepts, with a difference that Liouville equation for the conditional probability distribution is introduced as a macroscopic constraint given by a phase space average. We consider the incomplete nature of our information about microscopic dynamics in a rational way that is consistent with Jaynes’ formulation of predictive statistical mechanics, and the concept of macroscopic reproducibility for time dependent processes. Maximization of the conditional information entropy subject to this macroscopic constraint leads to a loss of correlation between the initial phase space paths and final microstates. Information entropy is the theoretic upper bound on the conditional information entropy, with the upper bound attained only in case of the complete loss of correlation. In this alternative approach to prediction of macroscopic time evolution, maximization of the conditional information entropy is equivalent to the loss of statistical correlation, and leads to corresponding loss of information. In accordance with the original idea of Jaynes, irreversibility appears as a consequence of gradual loss of information about possible microstates of the system.

Collective mode dispersions of organic chain compounds

We investigate the collective mode dispersions for the tight-binding dielectric matrix with two one-dimensional electron bands per donor and acceptor chains, and the three-dimensional long-range Coulomb electron-electron interaction within the random phase approximation. The hybridized collective modes are the result of the strong coupling between the intraband plasmon and the interband dipolar modes due to strong dipole Coulomb interactions. Our calculations show the existence of the low-energy renormalized plasmon mode above the electron-hole quasi-continuum in the long wavelength limit. The obtained modes are brought into correspondence with the optical data of quasi-one-dimensional organic conductor tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ). Namely, the renormalized plasmon and the dipolar mode are assigned to the observed excitations at respective energy scales of roughly 10 meV and 0.75 eV, explaining why lower excitation is eliminated while higher excitation persists below the temperature of the Peierls phase transition.

Relation between Boltzmann and Gibbs entropy and example with multinomial distribution

General relationship between mean Boltzmann entropy and Gibbs entropy is established. It is found that their difference is equal to fluctuation entropy, which is a Gibbs-like entropy of macroscopic quantities. The ratio of the fluctuation entropy and mean Boltzmann, or Gibbs entropy vanishes in the thermodynamic limit for a system of distinguishable and independent particles. It is argued that large fluctuation entropy clearly indicates the limit where standard statistical approach should be modified, or extended using other methods like renormalization group.

Dielectric response of metallic crystal made up of highly polarisable molecules: the semi-classical approach

The dielectric response is considered within models of a one-band metal, a two-band insulator and a two-band metal using the semi-classical approximation. Corresponding dielectric functions are found. The dielectric function of two-band metal is found to be the interpolation between the Sellmeyer and Lorenz-Lorentz expressions, respectively. The frequencies of the collective modes are identified as the zeroes of the dielectric functions. The correspondence between the semi-classical approach used in this paper and the many-body calculation within the random-phase approximation is established.