Molecular properties via a subsystem density functional theory formulation: a common framework for electronic embedding.
In this article, we present a consistent derivation of a density functional theory (DFT) based embedding method which encompasses wave-function theory-in-DFT (WFT-in-DFT) and the DFT-based subsystem formulation of response theory (DFT-in-DFT) by Neugebauer [J. Neugebauer, J. Chem. Phys. 131, 084104 (2009)] as special cases. This formulation, which is based on the time-averaged quasi-energy formalism, makes use of the variation Lagrangian techniques to allow the use of non-variational (in particular: coupled cluster) wave-function-based methods. We show how, in the time-independent limit, we naturally obtain expressions for the ground-state DFT-in-DFT and WFT-in-DFT embedding via a local potential. We furthermore provide working equations for the special case in which coupled cluster theory is used to obtain the density and excitation energies of the active subsystem. A sample application is given to demonstrate the method.
Amsterdam Center for Multiscale Modeling (ACMM), VU University Amsterdam, Theoretical Chemistry, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands. s.hoefener@vu.nl
Sebastian
S
Höfener
André Severo Pereira
AS
Gomes
Lucas
L
Visscher
D004583:Electrons; D011789:Quantum Theory