Local embedding of coupled cluster theory into the random phase approximation using plane waves.

Abstract

We present an embedding approach to treat local electron correlation effects in periodic environments. In a single consistent framework, our plane wave based scheme embeds a local high-level correlation calculation [here, Coupled Cluster (CC) theory], employing localized orbitals, into a low-level correlation calculation [here, the direct Random Phase Approximation (RPA)]. This choice allows for an accurate and efficient treatment of long-range dispersion effects. Accelerated convergence with respect to the local fragment size can be observed if the low-level and high-level long-range dispersions are quantitatively similar, as is the case for CC in RPA. To demonstrate the capabilities of the introduced embedding approach, we calculate adsorption energies of molecules on a surface and in a chabazite crystal cage, as well as the formation energy of a lattice impurity in a solid at the level of highly accurate many-electron perturbation theories. The absorption energy of a methane molecule in a zeolite chabazite is converged with an error well below 20 meV at the CC level. As our largest periodic benchmark system, we apply our scheme to the adsorption of a water molecule on titania in a supercell containing more than 1000 electrons.