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) https://doi.org/10.1063/1.3212883] 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.
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28 January 2012
Research Article|
January 24 2012
Molecular properties via a subsystem density functional theory formulation: A common framework for electronic embedding
Sebastian Höfener;
Sebastian Höfener
a)
1Amsterdam Center for Multiscale Modeling (ACMM),
VU University Amsterdam
, Theoretical Chemistry, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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André Severo Pereira Gomes;
André Severo Pereira Gomes
b)
2Laboratoire PhLAM, CNRS UMR 8523,
Université de Lille 1
, Bât P5, F-59655 Villeneuve d'Ascq Cedex, France
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Lucas Visscher
Lucas Visscher
c)
1Amsterdam Center for Multiscale Modeling (ACMM),
VU University Amsterdam
, Theoretical Chemistry, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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a)
Electronic mail: [email protected].
b)
Electronic mail: [email protected].
c)
Author to whom correspondence should be addressed. Electronic mail: [email protected].
J. Chem. Phys. 136, 044104 (2012)
Article history
Received:
August 31 2011
Accepted:
December 19 2011
Citation
Sebastian Höfener, André Severo Pereira Gomes, Lucas Visscher; Molecular properties via a subsystem density functional theory formulation: A common framework for electronic embedding. J. Chem. Phys. 28 January 2012; 136 (4): 044104. https://doi.org/10.1063/1.3675845
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