Efficient Treatment of Correlation Energies at the Basis-Set Limit by Monte Carlo Summation of Continuum States

[Image: see text] The calculation of electron correlation is vital for the description of atomistic phenomena in physics, chemistry, and biology. However, accurate wavefunction-based methods exhibit steep scaling and often sluggish convergence with respect to the basis set at hand. Because of their delocalization and ease of extrapolation to the basis-set limit, plane waves would be ideally suited for the calculation of basis-set limit correlation energies. However, the routine use of correlated wavefunction approaches in a plane-wave basis set is hampered by prohibitive scaling due to a large number of virtual continuum states and has not been feasible for all but the smallest systems, even if substantial computational resources are available and methods with comparably beneficial scaling, such as the Møller–Plesset perturbation theory to second order (MP2), are used. Here, we introduce a stochastic sampling of the MP2 integrand based on Monte Carlo summation over continuum orbitals, which allows for speedups of up to a factor of 1000. Given a fixed number of sampling points, the resulting algorithm is dominated by a flat scaling of [Image: see text]. Absolute correlation energies are accurate to <0.1 kcal/mol with respect to conventional calculations for several hundreds of electrons. This allows for the calculation of unbiased basis-set limit correlation energies for systems containing hundreds of electrons with unprecedented efficiency gains based on a straightforward treatment of continuum contributions.