(Received October 26, 1959)
In the pair-correlation, or quasi-chemical equilibrium, approximation to statistical mechanics, there appears the possibility of a condensation phenomenon closely analogous to a Bose-Einstein condensation of correlated pairs of particles. However, the expansion used in earlier work to establish this phenomenon fails to yield an adequate approximation at and below the condensation point. In this paper, we give an alternative development, first formally for an arbitrary number of quantum states of the pair, then carry out in detail for the case of only one, or only two, quantum states of the pair. It is shown that, in spite of the Fermi-Dirac statistics of the particles making up the pairs, it is nevertheless possible to accomodate an arbitrarily large number of particles within a single pair state. Furthermore, if two quantum states of the pair are possible, and conditions are such that either the pair state would be occupied by a macroscopic number of particles if it alone were present, then the Pauli exclusion principle works in such a way that the lower one of the two pair states is occupied by a macroscopic number of particles, whereas the occupation number of the upper pair state remains independent of the volume. This result is not restricted to pairs whose mean separation exceeds their internal size, but applies also to pairs which completely overlap each other. The result is therefore of significance in the theory of superconductivity where the electron pairs have an internal size of the order of the Pippard coherence length, which is much larger than the mean separation of their centres of gravity.
URL : http://ptp.ipap.jp/link?PTP/23/451/
DOI : 10.1143/PTP.23.451