Approximate Functional Integral Methods in Statistical Mechanics. I. Moment Expansions

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