Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory

Abstract

We present a simple and efficient embedding scheme for the wave-function based calculation of the energies of local excitations in large systems. By introducing an embedding potential obtained from density-functional theory (DFT) it is possible to describe the effect of an environment on local excitations of an embedded system in wave-function theory (WFT) calculations of the excitation energies. We outline the implementation of such a WFT-in-DFT embedding procedure employing the ADF, Dalton and DIRAC codes, where the embedded subsystem is treated with coupled cluster methods. We then evaluate this procedure in the calculation of the solvatochromic shift of acetone in water and of the f–fspectrum of NpO₂²⁺ embedded in a Cs₂UO₂Cl₄ crystal and find that our scheme does effectively incorporate the environment effect in both cases. A particularly interesting finding is that with our embedding scheme we can model the equatorial Cl⁻ ligands in NpO₂Cl₄²⁻ quite accurately, compared to a fully wavefunction-based calculation, and this opens up the possibility of modeling the interaction of different ligands to actinyl species with relatively high accuracy but at a much reduced computational cost.