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 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 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 hierarchy of equations for reduced density matrices relevant to thermodynamic equilibrium with account taken of the spin obtained earlier is modified in order to describe the state of a Fermi system with a condensate. Although the procedure is to some extent analogous with the one carried out by the author earlier for a Bose liquid peculiarities relevant to Fermi statistics complicate considerably the treatment. As in the case of the Bose liquid the condensate phase can be superfluid as well as nonsuperfluid, the physical causes of superfluidity being identical. A new mechanism of fermion pairing that acts even in the case of a purely repulsive Hamiltonian is pointed out. Special attention is given to the thermodynamics of a superfluid Fermi system. The example of a hard-sphere system is used to find out the form of phase diagrams, the character of the phase transition to a condensate phase and the properties of the last. Noticeable dissimilarities from a Bose system with the same Hamiltonian are revealed. Application of the present approach to superconductivity is discussed as well.
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 hierarchy of equations for reduced density matrices that describes a thermodynamically equilibrium quantum system obtained earlier by the author is investigated in the momentum representation. In the paper it is shown that the use of the momentum representation opens up new opportunities in studies of macroscopic quantum systems both nonsuperfluid and superfluid. It is found that the distribution over momenta in a quantum fluid is not a Bose or Fermi distribution even in the limit of practically noninteracting particles. The distribution looks like a Maxwellian one although, strictly speaking, it is not Maxwellian. The momentum distribution in a quantum crystal depends upon the interaction potential and the crystalline structure. The momentum distribution in a superfluid contains a delta function. The momentum distribution for the condensate in a superfluid crystal consists of delta peaks that are arranged periodically in momentum space. The periodical structure remains if the condensate crystal is not superfluid.
We state in the following a structure theory of the density matrices from the standpoint of secind quantization. The difficulties involved in the quantum-mechanical many body problem have so far proved to be so tremendous that as yet some have been obliged to stop before exact treatments and others have retired to phenomenological model theories. There are two main tools to approach the problem, the theory of second quantization and the theory of density matrix. The former, in spite of its generality and compactness, has never revealed us its adaptability to the practical problems of quantum statistical mechanics. In fact, about the exchange effect, namely the statistical correlation of particles, the latter informs us the detailed features of it by application of the group theory, while the former lacks, at present, such an exposition. For a long time a more general and simpler formulation than the current group theoretic method has been desired in the theoretical researches of spectroscopy. A distinguished contribution has been made by P. Jordan (1934) and H. Ostertag (1937) from the standpoint of second quantization. H. Ostertag made use of the theory of hypercomplex ring and introdeced the original concept of the elementary algebra. (Part II) Since the latter part of his formulation, however, seems to be complicated, it will be better, for clearness' sake, to avoid this part. Accordingly the concepts of the elementary algebra and the symmetric algebra will be introduced as a remedy for it. Then we shall complete our theory to include the whole theory of symmetric group. These concepts will serve to clarify and generalize the previous formulations and to unify the several group theoretic standpoints of the spectroscopy. In §1 and §2 the representation of the quantized density of Bose or Fermi particles will reveal itself as the density matrix of Bose or Fermi particles or as the density matrix of many electrons with a certain term of spin multiplets. Indeed, the theory of the statistical operator, or the density matrix of J. von Neumann and P.A.M. Dirac, the equilibrium properties of which have been fully examined by one of the authors (1940), is the natural formalism of dealing with quantum gases. A contribution has been made by W. Kofink (1938) to introduce the intrinsic degrees of freedom of particles. This attempt has resulted in a fair seccess. His formulation consists in making use of the initial stages of the theory of spectroscopy, which will be reexamined in the second section and Part II. In §3, as an example at zero temperature, the Hartree-Fock equation for a prescribed orbital and spin configuration will be derived, and in §4 some properties of the reduced density matrix will be illustrated.
We state in the following a structure theory of the density matrices from the standpoint of secind quantization. The difficulties involved in the quantum-mechanical many body problem have so far proved to be so tremendous that as yet some have been obliged to stop before exact treatments and others have retired to phenomenological model theories. There are two main tools to approach the problem, the theory of second quantization and the theory of density matrix. The former, in spite of its generality and compactness, has never revealed us its adaptability to the practical problems of quantum statistical mechanics. In fact, about the exchange effect, namely the statistical correlation of particles, the latter informs us the detailed features of it by application of the group theory, while the former lacks, at present, such an exposition. For a long time a more general and simpler formulation than the current group theoretic method has been desired in the theoretical researches of spectroscopy. A distinguished contribution has been made by P. Jordan (1934) and H. Ostertag (1937) from the standpoint of second quantization. H. Ostertag made use of the theory of hypercomplex ring and introdeced the original concept of the elementary algebra. (Part II) Since the latter part of his formulation, however, seems to be complicated, it will be better, for clearness' sake, to avoid this part. Accordingly the concepts of the elementary algebra and the symmetric algebra will be introduced as a remedy for it. Then we shall complete our theory to include the whole theory of symmetric group. These concepts will serve to clarify and generalize the previous formulations and to unify the several group theoretic standpoints of the spectroscopy. In §1 and §2 the representation of the quantized density of Bose or Fermi particles will reveal itself as the density matrix of Bose or Fermi particles or as the density matrix of many electrons with a certain term of spin multiplets. Indeed, the theory of the statistical operator, or the density matrix of J. von Neumann and P.A.M. Dirac, the equilibrium properties of which have been fully examined by one of the authors (1940), is the natural formalism of dealing with quantum gases. A contribution has been made by W. Kofink (1938) to introduce the intrinsic degrees of freedom of particles. This attempt has resulted in a fair seccess. His formulation consists in making use of the initial stages of the theory of spectroscopy, which will be reexamined in the second section and Part II. In §3, as an example at zero temperature, the Hartree-Fock equation for a prescribed orbital and spin configuration will be derived, and in §4 some properties of the reduced density matrix will be illustrated.