This topical review describes the methodology of continuum variational and diffusion quantum Monte Carlo calculations. These stochastic methods are based on many-body wavefunctions and are capable of achieving very high accuracy. The algorithms are intrinsically parallel and well suited to implementation on petascale computers, and the computational cost scales as a polynomial in the number of particles. A guide to the systems and topics which have been investigated using these methods is given. The bulk of the article is devoted to an overview of the basic quantum Monte Carlo methods, the forms and optimization of wavefunctions, performing calculations under periodic boundary conditions, using pseudopotentials, excited-state calculations, sources of calculational inaccuracy, and calculating energy differences and forces.

A form of Jastrow factor is introduced for use in quantum Monte Carlo simulations of finite and periodic systems. Test data are presented for atoms, molecules, and solids, including both all-electron and pseudopotential atoms. We demonstrate that our Jastrow factor is able to retrieve a large fraction of the correlation energy

The ground-state electronic structure of NiO and MnO has been calculated within the Hartree-Fock approximation using local Gaussian basis sets. For both, a qualitatively correct ground-state electronic structure is obtained in which the wide-band-gap insulating character of these materials is seen to be a result of large on-site Coulomb interactions. The materials are correctly predicted to be antiferromag- Recent experimental and theoretical evidence has led to the speculation that the upper valence band in these materials is primarily 0 2p in character. " This has important consequences regarding both the nature of hole states and the valency of the higher oxides, and has led to the suggested classification of NiO as a chargetransfer insulator. '

An inhomogeneous backflow transformation for many-particle wave functions is presented and applied to electrons in atoms, molecules, and solids. We report variational and diffusion quantum Monte Carlo (VMC and DMC) energies for various systems and study the computational cost of using backflow wave functions. We find that inhomogeneous backflow transformations can provide a substantial increase in the amount of correlation energy retrieved within VMC and DMC calculations. The backflow transformations significantly improve the wave functions and their nodal surfaces.

We illustrate through explicit numerical calculations how the Born rule probability densities of non-relativistic quantum mechanics emerge naturally from the particle dynamics of de Broglie-Bohm pilot-wave theory. The time evolution of a particle distribution initially not equal to the absolute square of the wave function is calculated for a particle in a two-dimensional infinite potential square well. Under the de BroglieBohm ontology, the box contains an objectively existing 'pilot wave' which guides the electron trajectory, and this is represented mathematically by a Schrödinger wave function composed of a finite out-of-phase superposition of M energy eigenstates (with M ranging from 4 to 64). The electron density distributions are found to evolve naturally into the Born rule ones and stay there; in analogy with the classical case this represents a decay to 'quantum equilibrium'. The proximity to equilibrium is characterized by the coarse-grained subquantum H -function which is found to decrease roughly exponentially towards zero over the course of time. The time scale t for this relaxation is calculated for various values of M and the coarse-graining length 3. Its dependence on M is found to disagree with an earlier theoretical prediction. A power law, t ∝ M −1 , is found to be fairly robust for all coarse-graining lengths and, although a weak dependence of t on 3 is observed, it does not appear to follow any straightforward scaling. A theoretical analysis is presented to explain these results. This improvement in our understanding of time scales for relaxation to quantum equilibrium is likely to be of use in the development of models of relaxation in the early Universe, with a view to constraining possible violations of the Born rule in inflationary cosmology.