How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations?

Humbert-Droz, Marie; Zhou, Xiuwen; Shedge, Sapana V.; Wesołowski, Tomasz Adam

doi:10.1007/s00214-013-1405-1

Cited by 54 publications

(76 citation statements)

References 99 publications

(204 reference statements)

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“…Numerical tests have shown, however, that in certain cases the inclusion of the solvent as a frozen density without relaxation through a FAT procedure, or only a partial relaxation without reaching full convergence, might already provide satisfactory results [40]. For systems where the full relaxation of all subsystems is necessary, FAT can be replaced by a much more computationally efficient procedure where all subsystems are optimized simultaneously, with a total density update at each SCF iteration [80][81][82].…”

Section: Outputmentioning

confidence: 99%

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

Krishtal

Sinha

Genova

et al. 2015

J. Phys.: Condens. Matter

113

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Subsystem Density-Functional Theory (DFT) is an emerging technique for calculating the electronic structure of complex molecular and condensed phase systems. In this topical review, we focus on some recent advances in this field related to the computation of condensed phase systems, their excited states, and the evaluation of many-body interactions between the subsystems. As subsystem DFT is in principle an exact theory, any advance in this field can have a dual role. One is the possible applicability of a resulting method in practical calculations. The other is the possibility of shedding light on some quantummechanical phenomenon which is more easily treated by subdividing a supersystem into subsystems. An example of the latter is many-body interactions. In the discussion, we present some recent work from our research group as well as some new results, casting them in the current state-of-the-art in this review as comprehensively as possible.2

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Section: Outputmentioning

confidence: 99%

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

Krishtal

Sinha

Genova

et al. 2015

J. Phys.: Condens. Matter

113

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“…Note that, if the embedding potential is treated exactly, Eqs. (17) and (18) admit in general multiple solutions [6,81,82]. Once the orbitals have been obtained, the total electron density is computed as…”

Section: Theorymentioning

confidence: 99%

Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals

Śmiga

Fabiano

Laricchia

et al. 2015

The Journal of Chemical Physics

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We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded systems. Meta-GGA functionals depend on the Kohn-Sham kinetic energy density (KED), which is not known as an explicit functional of the density. Therefore, they cannot be directly applied in subsystem DFT calculations. We propose a Laplacian-level approximation to the KED which overcomes the problem and provides a simple and accurate way to apply meta-GGA exchange-correlation functionals in subsystem DFT calculations. The so obtained density and energy errors, with respect to the corresponding supermolecular calculations, are comparable with conventional approaches, depending almost exclusively on the approximations in the non-additive kinetic embedding term. An embedding energy error decomposition explains the accuracy of our method.

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“…According to the analysis provided in Ref. 28, simultaneous optimization of ρ A and ρ B reflects both the physical effect of electronic polarization and the artificial effect -minimization of the error in the approximation to the non-additive kinetic energy functional.…”

Section: B Euler-lagrange Equations For the Embedded Wavefunction: Ementioning

confidence: 99%

Embedding potentials for excited states of embedded species

Wesołowski

2014

The Journal of Chemical Physics

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Frozen-Density-Embedding Theory (FDET) is a formalism to obtain the upper bound of the groundstate energy of the total system and the corresponding embedded wavefunction by means of EulerLagrange equations [T. A. Wesolowski, Phys. Rev. A 77(1), 012504 (2008)]. FDET provides the expression for the embedding potential as a functional of the electron density of the embedded species, electron density of the environment, and the field generated by other charges in the environment. Under certain conditions, FDET leads to the exact ground-state energy and density of the whole system. Following Perdew-Levy theorem on stationary states of the ground-state energy functional, the other-than-ground-state stationary states of the FDET energy functional correspond to excited states. In the present work, we analyze such use of other-than-ground-state embedded wavefunctions obtained in practical calculations, i.e., when the FDET embedding potential is approximated. Three computational approaches based on FDET, that assure self-consistent excitation energy and embedded wavefunction dealing with the issue of orthogonality of embedded wavefunctions for different states in a different manner, are proposed and discussed.

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How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations?

Cited by 54 publications

References 99 publications

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals

Embedding potentials for excited states of embedded species

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