Subsystem-Based GW/Bethe-Salpeter Equation.

ABSTRACT

Subsystem Density-Functional Theory and its extension to excited states, namely, subsystem Time-Dependent Density-Functional Theory, have been proven to be efficient and accurate fragmentation approaches for ground and excited states. In the present study we extend this approach to the subsystem-based description of total systems by means of GW and the Bethe-Salpeter equation (BSE). For this, we derive the working equations starting from a subsystem-based partitioning of the screened-Coulomb interaction for an arbitrary number of subsystems. Making use of certain approximations, we develop a parameter-free approach in which environmental screening contributions are effectively included for each subsystem. We demonstrate the applicability of these approximations by comparing quasi-particle energies and excitation energies from subsystem-based GW/BSE calculations to the supermolecular reference. Furthermore, we demonstrate the computational efficiency and the usefulness of this method for the description of photoinduced processes in complex chemical environments.