Projection-Based Correlated Wave Function in Density Functional Theory Embedding for Periodic Systems.

Abstract

We present a level shift projection operator-based embedding method for systems with periodic boundary conditions-where the "active" subsystem can be described using either density functional theory (DFT) or correlated wave function (WF) methods and the "environment" is described using DFT. Our method allows for k-point sampling, is shown to be exactly equal to the canonical DFT solution of the full system under the limit that we use the full system basis to describe each subsystem, and can treat the active subsystem either with periodic boundary conditions-in what we term "periodic-in-periodic" embedding-or as a molecular cluster-in "cluster-in-periodic" embedding. We explore each of these methods and show that cluster WF-in-periodic DFT embedding can accurately calculate the absorption energy of CO on to a Si(100)-2×1 surface.