A theory of non-equilibrium thermodynamics is developed. The general method to derive the closed set of kinetic equations for expectation values of physical quantities is developed, by making use of the functional Taylor expansion with respect to expectation values of physical quantities around the reference state. For this purpose, a definition of the thermodynamic state in the system whose state changes with time is presented in order to describe the general state of the many-body system from the unified point of view. The statistical mechanical probability distribution functions for the quantum-mechanical expectation values at the stationary state are developed, without making use of the concept of the constant of the motion. The relation between the expectation value and the most probable value for the probability distribution function is discussed, and it is found that both values are equivalent to each other, if the system is extended infinitely in space and time. Thus the condition for the thermodynamic limit may be defined in a generalized way. Our method is looked as a perturbational one in the equilibrium statistical mechanics, though the choice of the reference state is arbitrary.
A theory of non-equilibrium thermodynamics is developed. The general method to derive the closed set of kinetic equations for expectation values of physical quantities is developed, by making use of the functional Taylor expansion with respect to expectation values of physical quantities around the reference state. For this purpose, a definition of the thermodynamic state in the system whose state changes with time is presented in order to describe the general state of the many-body system from the unified point of view. The statistical mechanical probability distribution functions for the quantum-mechanical expectation values at the stationary state are developed, without making use of the concept of the constant of the motion. The relation between the expectation value and the most probable value for the probability distribution function is discussed, and it is found that both values are equivalent to each other, if the system is extended infinitely in space and time. Thus the condition for the thermodynamic limit may be defined in a generalized way. Our method is looked as a perturbational one in the equilibrium statistical mechanics, though the choice of the reference state is arbitrary.
Entropy in nonequilibrium statistical mechanics is investigated theoretically so as to extend the well-established equilibrium framework to open nonequilibrium systems. We first derive a microscopic expression of nonequilibrium entropy for an assembly of identical bosons/fermions interacting via a two-body potential. This is performed by starting from the Dyson equation on the Keldysh contour and following closely the procedure of Ivanov, Knoll and Voskresensky [Nucl. Phys. A {\bf 672} (2000) 313]. The obtained expression is identical in form with an exact expression of equilibrium entropy and obeys an equation of motion which satisfies the H-theorem in a limiting case. Thus, entropy can be defined unambiguously in nonequilibrium systems so as to embrace equilibrium statistical mechanics. This expression, however, differs from the one obtained by Ivanov {\em et al}., and we show explicitly that their ``memory corrections'' are not necessary. Based on our expression of nonequilibrium entropy, we then propose the following principle of maximum entropy for nonequilibrium steady states: ``The state which is realized most probably among possible steady states without time evolution is the one that makes entropy maximum as a function of mechanical variables, such as the total particle number, energy, momentum, energy flux, etc.'' During the course of the study, we also develop a compact real-time perturbation expansion in terms of the matrix Keldysh Green's function.
A possible thermodynamic evolution to equilibrium of a quantum statistical system is discussed. The description is entirely algebraic and it is done by means of complex coherent states built in the Universal Enveloping Algebra of the complex algebra https://www.w3.org/1998/Math/MathML" display="inline"> A 1 . Finite dimensional representations of https://www.w3.org/1998/Math/MathML" display="inline"> A 1 give fermion distributions while infinite dimensional ones describe bosons. The scheme is thermodynamic in the sense that fluctuations are not considered and this allows us to resort to an evolution operator that realizes, for t → ∞, a projector on the state of equilibrium. The shrinking of the Hilbert space is related to non unitary evolution that change the normalization of the state vectors. The theory is invariant under time reversal: vectors at t → ±∞ differ only in phases and both correspond to the equilibrium probability distribution. Equilibrium and non-equilibrium thermodynamic quantities can be calculated at microscopic level in a framework that is in between thermodynamic and statistical mechanics. Our approach is a physically founded example of non-linear quantum theory.
We establish a rather deep relation between statistical mechanics and quantum mechanics at an imaginary time. For the quantum field theory, this implies a relation between finite temperature quantum field theory in Minkowski space and quantum field theory in Euclidean space with one compact Euclidean time direction. The quantum mechanical language being a proper formulation of statistical physics as a molecular theory is basically the study of quantum equilibrium as well as non-equilibrium systems. A quantum system found in a thermodynamic equilibrium state with an external classical system (thermostat or thermal reservoir) may be characterized by fixed values of thermodynamic parameters of the system, say, for example, temperature T , volume V and number of particles N . In this way the total energy of the thermostat is assumed to be much greater than the energy of the system. The behavior of the quantum system may be assumed to be independent of the nature of the thermostat. The most convenient object of the quantum theory to describe such non-isolated systems is the density matrix since the partition function does not determine any local thermodynamic quantities. It is for this reason that we introduced quantum mechanical and quantum statistical density matrices which are necessary to do the investigation via path integration. This enables us to make a transition to the quasi-classical approximation of quantum statistical mechanics, which, in turn, enables us to evaluate the first quantum correction to the classical Boltzmann distribution function.
Historically, thermodynamics was formulated for macroscopic systems followed by the development of statistical mechanics which provided microscopic formulations for quantities such as entropy. Entropy is traditionally linked to the ln of the number states available or to the Shannon’s form -k Sum over i P(ei) ln(P(ei)) where P(ei) is the probability for the quantity ei. In addition a variable T (linked to average kinetic energy) appears in both theories. Later the Schrodinger equation was developed to describe bound electron states in an atom etc. These states were characterized by a math object W(x) called the wavefunction and a set of discrete energy levels was calculated which matched data of emitted photons. In a previous note (1) we argued that the average energy En for a quantum bound state plays the same role of characterizing equilibrium as T in classical thermodynamics/statistical mechanics. We further argued that En is linked to parameters in the system. For example, for a particle in a box with infinite potential walls, En is linked to L as well as to n the energy level. One may change En by either changing n or L separately (or both). Holding L constant and changing n leads to a certain type of energy change. We argue this is similar to holding the volume of a gas constant and increasing T. Alternatively, one may leave n unchanged (a quantum adiabatic process) and change L i.e. a mechanical change or work. We argue that one may already consider the concept of the first law of thermodynamics at the quantum bound state level i.e. dE = dQ - dWork where Work is linked to a change in a physical parameter, such as L the length of the box, whereas dQ is linked to energy changes not involving a physical parameter e.g. a change in n the energy level. The Schrodinger equation yields solutions for W(x)=Sum over p a(p)exp(ipx) the wavefunction as well as En’s. We have argued in previous notes that W(x) is part of a conditional probability P(p/x)= a(p)exp(ipx)/W(x) and that En is constant at each point x just as T is constant at each x for classical statistical equilibrium (1). Thus a kind of statistical mechanics exists at the wavefunction level we argue. This statistical mechanics makes use of a free particle wavefunction exp(ipx) and weights a(p), but does not contain the usual P(x), P(p) picture of the classical world. We have shown in (2) that one may obtain P(x)=W*(x)W(x) and P(p)=a*(p)a(p) from the conditional probability. The essential physics we argue, however, is at the level of the wavefunction together with its own unique statistical scenario of exp(ipx)’s interacting with exp(ikx)’s from V(x)=Sum over Vkexp(ikx) (see (1)). Given that P(x) and P(p) exist for a quantum bound state, it may be convenient to use them in formulas because they are linked to a classical statistical picture. We argue that one may use P(x) and P(p) to construct an object S such that T dS does not change when one changes L, the size of box with infinite potential walls. We argue that such an object follows from properties of the Schrodinger equation together with various assumptions. We arrive at S=Sp+Sx where Sp=-k Integral dp a(p)a(p) ln{|a(p)a(p)}| and Sx= -k Integral dx W(x)W(x) ln(W(x)W(x)) for a given energy level. We do not use arguments related to taking ln of the number of states present or Shannon’s entropy. Rather we look for a solution which does not depend on L and is additive. We note, however, that for both W(x)W(x) and a(p)a(p) the solution found is mathematically consistent with the entropy form found by considering independent probabilities. This, however, applies to P(x) and P(p), but we argue that the physical situation is based on W(x) and a(p) as solutions of the Schrodinger equation. Nevertheless P(x) and P(p) are physical observables and not simply math constructs and so may think of them in a somewhat classical manner in terms of probability. Thus we argue that thermodynamics is already present at the level of a quantum bound state and that one may obtain Shannon’s entropy at this level using P(x) and P(p), but without considering the overall probability of independent probabilities as in information theory or numbers of states. Rather obtaining a function which is additive in Sp and Sx and eliminates L is the main consideration. We also argue that S=Sp+Sx carries over into mixed quantum state wavefunctions even though it is usually ignored. Thus we try to argue that it is the bound quantum state which gives rise to the notion of thermodynamics and entropy.
The science of thermodynamics was put together in the Nineteenth Century to describe large systems in equilibrium. One part of thermodynamics defines entropy for equilibrium systems and demands an ever-increasing entropy for non-equilibrium ones. However, starting with the work of Ludwig Boltzmann in 1872, and continuing to the present day, various models of non-equilibrium behavior have been put together with the specific aim of generalizing the concept of entropy to non-equilibrium situations. This kind of entropy has been termed {\em kinetic entropy} to distinguish it from the thermodynamic variety. Knowledge of kinetic entropy started from Boltzmann's insight about his equation for the time dependence of gaseous systems. In this paper, his result is stated as a definition of kinetic entropy in terms of a local equation for the entropy density. This definition is then applied to Landau's theory of the Fermi liquid thereby giving the kinetic entropy within that theory. Entropy has been defined and used for a wide variety of situations in which a condensed matter system has been allowed to relax for a sufficient period so that the very most rapid fluctuations have been ironed out. One of the broadest applications of non-equilibrium analysis considers quantum degenerate systems using Martin-Schwinger Green's functions\cite{MS} as generalized of Wigner functions, $g^$. This paper describes once again these how the quantum kinetic equations for these functions give locally defined conservation laws for mass momentum and energy. In local thermodynamic equilibrium, this kinetic theory enables a reasonable local definition of entropy density. However, when the system is outside of local equilibrium, this definition fails. It is speculated that quantum entanglement is the source of this failure.
The author presents his experience in teaching at a graduate level the quantal exposition of a new non-statistically based paradigm of physics and thermodynamics. This paradigm, called the Unified Quantum Theory of Mechanics and Thermodynamics, applies to all systems large or small (including one particle systems) either in a state of thermodynamic (i.e. stable) equilibrium or not in a state of thermodynamic equilibrium. It uses as its primitives inertial mass, force, and time and introduces the laws of thermodynamics in the most unambiguous and general formulations found in the literature. Starting with a precise definition of system and of state followed by statements and corollaries of the laws of thermodynamics, the thermodynamic formalism is developed without circularity and ambiguity. In this quantal exposition of the new paradigm, a brief review of the formalism of thermodynamics as a general science not limited to stable equilibrium and large (macroscopic) systems as well as a very brief summary of the three prevalent formalisms in classical physics are presented followed by a presentation and development of solutions for a number of elementary problems in quantum physics (e.g., a particle in a box, a harmonic oscillator, a rigid rotor, etc.). These solutions and the maximum entropy principle are then used in a constrained optimization to develop the canonical and grand canonical distributions for Fermi-Dirac and Bose-Einstein types of particles, i.e. for fermions and bosons. This is done without the use of analogies between statistical and thermodynamic results and without additional hypotheses such as the ergodic hypothesis of statistical mechanics. These distributions are then employed under various assumptions (i.e. the Boltzmann, constant-potential, point-particle, and continuous eigenvalue-spectrum approximations) to derive the corresponding thermodynamic property expressions for perfect, semi-perfect (ideal), and Sommerfeld gases as well as for mixtures of ionized and dissociated gases. In a similar fashion but with a change from a single- to a multi-particle partition function and with the addition of various inter-particle potentials for two-particle interactions (e.g., the Lennard-Jones potential, the square-well potential, etc.), expressions for the thermodynamic properties of dense gases are developed and presented.An initial version of this paper was published inJuly of 2006 in the proceedings of ECOS’06, AghiaPelagia, Crete, Greece.