Thermodynamical functions are expressed by perturbation theory as stationary functionals of the 1-, and 2-body potentials; the stationary conditions yield the 1-, and 2-body correlation functions in terms of the potentials. Through the use of diagramatic methods, it is possible to explicitly invert these relations and express the potentials in terms of the correlation functions; in turn the thermo-dynamical functions become stationary functionals of the correlation functions. This procedure is carried out for normal (quantum and classical) systems. For superfluid systems, 12−,32− body potentials, and correlation functions need also be considered and the above procedure becomes imperative to eliminate the nonphysical 12−,32− body potentials. Its first two steps are illustrated, and various features of this formulation and its usefulness are discussed.
Thermodynamical functions are expressed by perturbation theory as stationary functionals of the 1-, and 2-body potentials; the stationary conditions yield the 1-, and 2-body correlation functions in terms of the potentials. Through the use of diagramatic methods, it is possible to explicitly invert these relations and express the potentials in terms of the correlation functions; in turn the thermo-dynamical functions become stationary functionals of the correlation functions. This procedure is carried out for normal (quantum and classical) systems. For superfluid systems, 12−,32− body potentials, and correlation functions need also be considered and the above procedure becomes imperative to eliminate the nonphysical 12−,32− body potentials. Its first two steps are illustrated, and various features of this formulation and its usefulness are discussed.
Quantum statistical mechanics is renormalized, that is, the thermodynamical functions and the ``bare'' ν-body potentials vν occurring in the Hamiltonian are expressed as functionals of the ν-body distribution functions Gν (the expectation values of 2ν field operators). The field operators are considered as having two components (creation and annihilation), and Gν thus has (2)2ν components. The renormalization is carried out for superfluid Bose systems for which it is necessary to consider the expectation values of 2ν = 1, 2, 3, 4 operators. Superfluid Fermi systems and normal systems appear as particular cases, described by expectation values of 2ν = 2, 4 operators. This problem, dealt with by algebraic methods in part I, is attacked here by diagrammatic methods. These methods are more dependent on convergence properties but the resulting functionals are obtained explicitly as power series of the Gν′s, the general term being represented by a class of diagrams characterized by their topological structure. In the final result, the entropy is exhibited as an explicit functional of the distribution functions Gν, (2ν = 1, 2, 3, 4), or more precisely, of functions directly related to them. This functional no longer involves the potentials (nor the equilibrium parameters). It is stationary under independent variations of the Gν′s, subject to the constraints of constant energy and particle number. The four equations of stationarity exhibit each function vν as a functional of the Gν′s, self-consistently defining these distribution functions.
This paper shows how the dynamical and thermodynamical properties of an interacting quantum mechanical system with many degrees of freedom may be expressed and calculated solely in terms of renormalized propagators and renormalized vertices or interactions. The formulation employed is sufficiently general to encompass systems which have several components, with Fermi or Bose statistics, whether or not they exhibit superfluidity or superconductivity. The process of renormalization is the functional generalization of the thermodynamic transformation from the chemical potential and temperature to the energy and matter densities. With each set of variables (here, functions) is associated a natural thermodynamic function (here a functional). The natural functional for the unrenormalized potentials which occur in the Hamiltonian is the logarithm of the grand partition function; the natural functional for the fully renormalized variables, the distribution functions, is the entropy. In particular, a stationarity principle for a functional F(2) of distribution functions subject to constraints is shown to provide a fully renormalized description of the system. The numerical value of this functional, at the stationarity point at which the distribution functions take their actual value, is the entropy of the system. The equations of stationarity are expressions for the unrenormalized ν-body potentials vν in terms of the ν′-body distribution functions Gν′. The functionals F(2) and vν (of the distribution functions Gν′) are expressed as the solutions of closed functional differential equations which may be used to generate their power-series expansions. For a superfluid Bose system, as for the electromagnetic field interacting with matter, it is necessary to consider expectation values of odd, as well as even, numbers of field operators. In particular it is necessary to employ the expectation values Gν for 2ν = 1, 2, 3, 4 field operators. For a fermion system, even if it is superconducting, only the functions Gν for 2ν = 2, 4 are required. In contrast to other thermodynamical functionals, the entropy functional F(2) makes no reference to equilibrium parameters such as temperature and chemical potential.
Certain problems connected with the choice of trial variational functions for the quantum many-body problem are discussed. It is convenient to make use of the reduced-density-matrix formulation developed by L\"owdin and Mayer, since a system whose Hamiltonian contains only 1- and 2-body interactions is characterized by the two simplest reduced density matrices ${\ensuremath{\Gamma}}^{(1)}$ and ${\ensuremath{\Gamma}}^{(2)}$. It is known that symmetry, Hermiticity, and normalizability conditions are not sufficient to ensure a physically realizable choice of the functions ${\ensuremath{\Gamma}}^{(1)}$ and ${\ensuremath{\Gamma}}^{(2)}$. However an additional nontrivial restriction is imposed by the fact that such functions must be possible variational extrema. The implications of this condition are investigated in some detail and it turns out that all the nonphysical choices of ${\ensuremath{\Gamma}}^{(1)}$ and ${\ensuremath{\Gamma}}^{(2)}$ which have been exhibited by various authors are eliminated. The condition is essentially nonquantum inasmuch as an analogous argument should be possible for a classical system. Moreover one of the consequences of this condition is that the system (classical or quantum) may exhibit macroscopic behavior, i.e., order-disorder transitions. The analysis leads to apparently reasonable choices of trial forms for ${\ensuremath{\Gamma}}^{(1)}$ and ${\ensuremath{\Gamma}}^{(2)}$, although it is still not known whether any further restriction must be imposed to complete the sufficiency argument.
An alternative approach for treating strongly interacting statistical systems with strongly singular potentials is developed. This approach combines both the advantages of decoupling procedures for Green functions, which eliminate divergences caused by singular potentials, and the advantages of perturbation theory, which is a regular procedure that makes it possible to construct subsequent approximations above the chosen decoupling. The resulting iterative sequence of Green functions generates corresponding sequences of observable quantities. To improve the convergence of the latter sequences a method is suggested based on the renormalization-group ideas. A simple illustration is given.
In the present paper, a generalization of the method of partial summation of the expansion of the thermodynamical potential is proposed. This generalization allows one to obtain the corresponding equations for higher-order correlation matrices, as well as to formulate the variational method for their solution. We show that correlation matrices of equilibrium quantum system satisfy a variational principle for thermodynamic potential which is functional of these matrices that provides a thermodynamic consistency of the theory. This result is similar to a variational principle for correlation functions of classical systems.
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.