David M. Ceperley

An exact stochastic simulation of the Schroedinger equation for charged bosons and fermions has been used to calculate the correlation energies, to locate the transitions to their respective crystal phases at zero temperature within 10%, and to establish the stability at intermediate densities of a ferromagnetic fluid of electrons.

One of Feynman's early applications of path integrals was to superfluid $^{4}\mathrm{He}$. He showed that the thermodynamic properties of Bose systems are exactly equivalent to those of a peculiar type of interacting classical "ring polymer." Using this mapping, one can generalize Monte Carlo simulation techniques commonly used for classical systems to simulate boson systems. In this review, the author introduces this picture of a boson superfluid and shows how superfluidity and Bose condensation manifest themselves. He shows the excellent agreement between simulations and experimental measurements on liquid and solid helium for such quantities as pair correlations, the superfluid density, the energy, and the momentum distribution. Major aspects of computational techniques developed for a boson superfluid are discussed: the construction of more accurate approximate density matrices to reduce the number of points on the path integral, sampling techniques to move through the space of exchanges and paths quickly, and the construction of estimators for various properties such as the energy, the momentum distribution, the superfluid density, and the exchange frequency in a quantum crystal. Finally the path-integral Monte Carlo method is compared to other quantum Monte Carlo methods.

The ground-state energies of H2, LiH, Li2, and H2O are calculated by a fixed-node quantum Monte Carlo method, which is presented in detail. For each molecule, relatively simple trial wave functions ΨT are chosen. Each ΨT consists of a single Slater determinant of molecular orbitals multiplied by a product of pair-correlation (Jastrow) functions. These wave functions are used as importance functions in a stochastic approach that solves the Schrödinger equation by treating it as a diffusion equation. In this approach, ΨT serves as a ‘‘guiding function’’ for a random walk of the electrons through configuration space. In the fixed-node approximation used here, the diffusion process is confined to connected regions of space, bounded by the nodes (zeros) of ΨT. This approximation simplifies the treatment of Fermi statistics, since within each region an electronic probability amplitude is obtained which does not change sign. Within these approximate boundaries, however, the Fermi problem is solved exactly. The energy obtained by this procedure is shown to be an upper bound to the true energy. For the molecular systems treated, at least as much of the correlation energy is accounted for with the relatively simple ΨT’s used here as by the best configuration interaction calculations presently available.

Variational and fixed-node Green's-function Monte Carlo calculations have been performed to find the ground-state properties of the two-dimensional electron gas in the density range 1\ensuremath{\le}${r}_{s}$\ensuremath{\le}100. Our calculations predict a Wigner crystallization at the density ${r}_{s}$\ensuremath{\simeq}37\ifmmode\pm\else\textpm\fi{}5. The electron system is found to be in the normal- (paramagnetic) fluid state below the transition density, but the fully polarized state is very close in energy. We have tabulated the values of pair distribution function g(r), the static structure factor S(k), and the momentum distribution n(k) at several densities of interest both in the normal and the polarized phases. An estimate of the spin susceptibility \ensuremath{\chi} is also given.

The Metropolis Monte Carlo method is used to sample the square of an antisymmetric wave function composed of a product of a Jastrow wave function and a number of Slater determinants. We calculate variational energies for $^{3}\mathrm{He}$ and several models of neutron matter. The first-order Wu-Feenberg expansion is shown always to underestimate the energy, sometimes seriously. The phase diagram for ground-state Yukawa matter is determined. There is a class of Yukawa potentials which do not lead to a crystal phase at any density.