The method of functional differentiation, used in classical statistical mechanics to obtain approximate integral equations for the pair distribution function, is extended to quantum systems obeying Maxwell-Boltzmann statistics. The grand partition function is written as a path integral, and space-temperature distributions are generated from it by successive functional differentiation. Distributions can be expanded in powers of an external potential via a functional Taylor series. When the series is truncated so that no distributions higher than second order enter and the external potential is specialized to one arising from a fixed particle in the system, coupled integral equations result for the two kinds of pair distributions. The first-order Ursell function calculated from these equations yields the Montroll-Ward ring summation for the grand potential. This approximate Ursell function determines also the Fourier transform of the momentum density (useful in calculating the p = 0 occupation number). Although divergences appear in the low-temperature limit, they can be removed by a simple modification of the independent functional. An extension to Fermi-Dirac and Böse-Einstein statistics is indicated at appropriate places in the text.
The method of functional differentiation, used in classical statistical mechanics to obtain approximate integral equations for the pair distribution function, is extended to quantum systems obeying Maxwell-Boltzmann statistics. The grand partition function is written as a path integral, and space-temperature distributions are generated from it by successive functional differentiation. Distributions can be expanded in powers of an external potential via a functional Taylor series. When the series is truncated so that no distributions higher than second order enter and the external potential is specialized to one arising from a fixed particle in the system, coupled integral equations result for the two kinds of pair distributions. The first-order Ursell function calculated from these equations yields the Montroll-Ward ring summation for the grand potential. This approximate Ursell function determines also the Fourier transform of the momentum density (useful in calculating the p = 0 occupation number). Although divergences appear in the low-temperature limit, they can be removed by a simple modification of the independent functional. An extension to Fermi-Dirac and Böse-Einstein statistics is indicated at appropriate places in the text.
In this paper, four distinct ideas are combined, which under a wide range of circumstances can give very rapidly converging series expansions for functional integrals. (1) Expansion of the functional being integrated in functional Taylor series. In the familiar case arising in quantum statistical mechanics, that of the Wiener integral of exp[−∫V(x(t))dt],V(x) being the perturbing potential, this is equivalent to expanding the characteristic functional of the probability functional of V(x(t)) in central moments of V(x(t)). The lowest-order term of the series is the approximation obtained by Feynman and Hibbs through a variational method. (2) Transfer of the harmonic term of the potential, when the functional integral is the quantum-statistical density matrix (Green's function of the Bloch equation), to the weighting function. This transforms the functional integral from a Wiener to an Uhlenbeck-Ornstein integral. The formal expressions for the terms of the expansion are somewhat more complicated, but they can be worked out, and the result is a great improvement in the speed of convergence of the series with decreasing temperature and/or decreasing relative magnitude of the anharmonic part of the potential. (3) ``Reservation of variables'' in the integration. This amounts to breaking the averaging process down into an average over subsets of the distributed random function (conditional average), followed by an averaging of these averages. Any step of this kind (it may be repeated within the subsets, etc.) gives an improvement of accuracy. (4) When the quantity being evaluated through functional integration is the partition function, the device introduced by Feynman and Hibbs, of interchanging the functional integration with the integration of the Green's function over the equated initial and final configuration-space points, may be combined with the above techniques. This eliminates one integration in the terms of the expansion and seems to improve accuracy at the same time. The general series obtained is correlated with more conventional operator techniques of quantum-mechanical perturbation theory, in order to answer the perennial question, does the path-integral method bring with it anything that could not be derived by other methods? It is in some sense a Feynman-Dyson expansion of the Green's function, but one that is further modified mathematically in a way characteristic only of the path-integral point of view, and which, moreover, improves its accuracy. It thus appears unlikely that the result is merely one of standard type disguised as a functional integral result. Sample numerical calculations are given to assay the accuracy of the methods, which are shown to compare very favorably with the traditional approximation of finite subdivision of the time interval.
The Bloch equation is utilized to derive an integro-differential equation for the temperature dependence of the Wigner distribution function of a canonical ensemble. This equation is solved by two methods; one yields a power series in Planck's constant and the other a power series in the potential energy of the system. Transformation functions for the density matrix and the Wigner function are discussed and their possible application in the treatment of systems obeying Fermi-Dirac or Bose-Einstein statistics is investigated.
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.
Abstract The focus of Chapter 12 is the Feynman path integral formulations of quantum mechanics and quantum statistical mechanics. The connection between real-time quantum propagator and the density matrix is established via the Wick rotation, and a Trotter expansion is used to derive discrete path integral expressions for both. The continuous limit of the discrete path integral is derived to yield the functional integral formulation of the path integral. The construction of estimators and their averages for computing quantum observables is discussed. Next, the path integral is extended to incorporate Boltzmann, Fermi-Dirac, and Bose-Einstein statistics, and a useful recursive formula for the partition function is derived that accelerates convergence by building up N-body partition functions from those of smaller systems. Quantum free energies are discussed, and algorithms for the evaluation of path integrals using molecular dynamics or Monte Carlo are presented. The chapter concludes with a discussion of higher-order factorizations and ring-polymer contraction methods to reduce the computational overhead of path-integral calculations
By expanding the grand partition function, we obtain the expression for partition function of two dimensional free particles which is seen to be of the same form as that of one dimensional harmonic oscillators. For such systems it is shown that the difference in statistics does not appear in thermal behavior. When the energy levels of the particles are modified as ε n 1 , n 2 = Δ + b ( n 1 2 + n 2 2 ), Δ >0, the Bose condensation occurs and, if we set Δ =2 b , the condensation temperature qualitatively agrees with that of Osborne. The speciffic heat of free Bosons in a narrow box is calculated as the function of temperature, its width d being taken 7.1 Å and 14.2 Å. The results show that the maximum of the specific heat occurs at higher temperatures than that of the case d =∞, and its height becomes lower. The weak excitation of a Fermi system can be treated as excitons which obey Bose statistics. And we can show, by the method analogous to that of Ward and Wilks and Dingle, that the sound wave in a Fermi gas should be considered as the second sound, or the propagation of fluctuation in exciton distribution. Its propagation velocity is shown to become p0/3m, where p 0 is the momentum at the Fermi surface.
Abstract. It is demonstrated that the statistical mechanical partition function can be used to construct various different forms of phase space distributions. This indicates that its structure is not restricted to the Gibbs–Boltzmann factor prescription which is based on counting statistics. With the widely used replacement of the Boltzmann factor by a generalised Lorentzian (also known as the q-deformed exponential function, where κ = 1∕|q − 1|, with κ, q ∈ R) both the kappa-Bose and kappa-Fermi partition functions are obtained in quite a straightforward way, from which the conventional Bose and Fermi distributions follow for κ → ∞. For κ ≠ ∞ these are subject to the restrictions that they can be used only at temperatures far from zero. They thus, as shown earlier, have little value for quantum physics. This is reasonable, because physical κ systems imply strong correlations which are absent at zero temperature where apart from stochastics all dynamical interactions are frozen. In the classical large temperature limit one obtains physically reasonable κ distributions which depend on energy respectively momentum as well as on chemical potential. Looking for other functional dependencies, we examine Bessel functions whether they can be used for obtaining valid distributions. Again and for the same reason, no Fermi and Bose distributions exist in the low temperature limit. However, a classical Bessel–Boltzmann distribution can be constructed which is a Bessel-modified Lorentzian distribution. Whether it makes any physical sense remains an open question. This is not investigated here. The choice of Bessel functions is motivated solely by their convergence properties and not by reference to any physical demands. This result suggests that the Gibbs–Boltzmann partition function is fundamental not only to Gibbs–Boltzmann but also to a large class of generalised Lorentzian distributions as well as to the corresponding nonextensive statistical mechanics.