The paper is devoted to further development of the new approach in equilibrium statistical mechanics the basis of which was worked out in a series of articles by the author. The approach proceeds on the use of a hierarchy of equations for reduced density matrices in the case of thermodynamic equilibrium. The present paper deals with a system containing particles of several kinds with arbitrary spin, for which the hierarchy obtained previously for a single-component system is generalized. Thermodynamics of the multicomponent system described by the hierarchy deduced is constructed as well.
The paper is devoted to further development of the new approach in equilibrium statistical mechanics the basis of which was worked out in a series of articles by the author. The approach proceeds on the use of a hierarchy of equations for reduced density matrices in the case of thermodynamic equilibrium. The present paper deals with a system containing particles of several kinds with arbitrary spin, for which the hierarchy obtained previously for a single-component system is generalized. Thermodynamics of the multicomponent system described by the hierarchy deduced is constructed as well.
The new approach in quantum statistical mechanics proposed by the author in previous publications is extended to systems of nonzero-spin particles. It is shown that properties of particles relevant to their spin can well be incorporated into the approach proposed. In so doing the principal ideas of the approach undergo no changes and lead to a hierarchy of equations for reduced density matrices at thermodynamic equilibrium that generalizes the hierarchy obtained earlier for spinless particles. Thermodynamics based on the hierarchy is worked out as well. The hierarchy and relevant thermodynamics enable one to calculate both thermodynamical properties of a system of particles and structural ones. With the help of perturbation expansions it is shown that the hierarchy has a solution and the solution is unique at least in the case of a weakly interacting system. Using the example of a hard-sphere system wherein triplet correlations are disregarded it is demonstrated that the hierarchy may serve as basis for deriving various results. Comparison of these results with results of other theoretical treatments evidences complete agreement within the limits allowed by the approximation used.
The hierarchy of the equations of motion for the reduced density matrices in quantum statistical mechanics is solved and the (cumulant) reduced density matrices at a time t are expressed in terms of those at an earlier time t0. Diagrams are introduced to express the results. With the aid of the technique of partial summations, the general term in the kinetic equation for the one-particle reduced density matrix or the generalized Boltzmann equation in quantum statistical mechanics is obtained. The equation is non-Markovian. A method of reducing the equation to Markovian is sketched.
The binary collision method of Lee and Yang is extended in order to investigate the statistical mechanics of a multicomponent mixture of interacting gases obeying Bose-Einstein or Fermi-Dirac statistics. First, the case of a mixture of two kinds of hard-sphere spinless bosons is studied and then the generalization is carried over to the case of a mixture of several components consisting of particles with arbitrary spin and statistics. An explicit derivation of the fugacity expansion, correct to the second order in the interaction parameters, is given. Expressions are derived for the second and third virial coefficients of the system and a discussion is given of the salient features of the results obtained. Finally, the case of a binary mixture, with one component consisting of bosons and the other of fermions, is considered and the phenomenon of Bose-Einstein condensation in this system is studied.
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.
This paper represents the full version of a paper published earlier in Physica A [246 (1997), 275]. The present paper includes argumentation, proofs and details omitted in the shortened version. The papers are a further development of the approach in quantum statistical mechanics proposed by the author. The hierarchy of equations for reduced density matrices obtained previously is extended to the case corresponding to the Bose-Einstein condensation. The relevant state of the system with a condensate can be superfluid as well as nonsuperfluid. Special attention is given to the thermodynamics of superfluid systems. According to the results of the papers superfluidity is the state of a fluid whose symmetry is spontaneously broken because of a stationary flow. The state corresponds to thermodynamic equilibrium while the magnitude of the flow depends upon the temperature and is determined by thermodynamic considerations. The equations obtained are solved in two simple cases. The physical origin of superfluidity, peculiarities of the phenomenon in closed volumes and the critical velocity are discussed as well.
Abstract It is well known that a new form of statistical mechanics has been recently developed by Einstein for an ideal gas of structureless mass-points. This starts from a discussion by Bose of the laws of temperature radiation based on the light quantum hypothesis, and has been further analysed by Schrödinger. Yet another new form has been proposed independently by Fermi and Dirac. The latter based his theory on a discussion of lightly coupled systems with the help of Schrödinger’s equation. Combined with Heisenberg’s work on the many-body problem, Dirac’s work forces us to conclude at least that the classical form of statistical mechanics must be changed. It indicates that the true form, which satisfies the laws of the new mechanics, is almost certainly that of Fermi and Dirac, which is the natural generalization of Pauli’s principle of exclusion for electronic orbits in an atom. The work of Heisenberg and Dirac already quoted has shown that Pauli’s principle and its extension are satisfied in the new mechanics by a complete self-consistent solution of the equations of motion. So far as I am aware, the discussions of the new forms have as yet dealt only with the statistics of a gas of structureless mass-points (and, of course, temperature radiation). There has, moreover, been as yet no attempt to define the entropy (and the absolute temperature) in strict analogy with rational thermodynamics by means of the equation dQ = TdS. If another definition is preferred, then this equation must be deduced from it. It has, therefore, seemed worth while to reopen the discussion by examining ab initio a quite general form of statistical mechanics of which the classical form and instein’s and Fermi-Dirac’s are special cases. This is rendered possible by using the powerful method of complex integration already applied to the classical form. The sequence of the argument is then to take the general form, which covers a very large range of ways of assigning possibilities and counting complexions, and construct on that basis exact integral expressions for the number of complexions possible to the assembly and for the average number of systems of the assembly in their various quantum states. We then derive from these the average energies and external reactions and so the form of dQ, deduce from dQ the existence of S and so define S and T. This can be done in the general form for assemblies of ideal systems just as general as can be handled in the classical way—ideal gases of molecules of any structure and crystals and radiation. Such assemblies are in all cases thermodynamical systems.