Stochastic self-consistent Green's function second-order perturbation theory (sGF2)

Abstract

The second-order Green's function method (GF2) was shown recently to be an accurate self-consistent approach for electronic structure of correlated systems since the self-energy accounts for both the weak and some of the strong correlation. The numerical scaling of GF2 is quite steep however, $O({N^5})$ (where the pre-factor is often hundreds), effectively preventing its application to large systems. Here, we develop a stochastic approach to GF2 (sGF2) where the self-energy is evaluated by a random-vector decomposition of Green's functions so that the dominant part of the calculation scales quasi linearly with system size. A study of hydrogen chains shows that the resulting approach is numerically efficient and accurate, as the stochastic errors are very small, 0.05% of the correlation energy for large systems with only a moderate computational effort. The method also yields automatically efficient MP2 energies and is automatically temperature dependent.