Orbital-Free Embedding Effective Potential in Analytically Solvable Cases

Savin, Andreas; Wesołowski, Tomasz Adam

doi:10.1007/978-90-481-2596-8_15

Cited by 17 publications

(24 citation statements)

References 37 publications

(43 reference statements)

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“…Properties of the embedding potential in analytically solvable cases have been investigated in Ref. [135], and an inversion technique for the determination of embedding potentials is presented in Ref. [136].…”

Section: Active Part and Environmentmentioning

confidence: 99%

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

2010

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Section: Active Part and Environmentmentioning

confidence: 99%

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

2010

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“…43,44 However, exact reference potentials for v T are so far only known for special limits-such as infinitely separated subsystems 43 or close to the nuclei of the frozen subsystems 44 -and for four-electron systems. 54 As a first step toward the development of improved approximations to v T , in this paper, we built on these efforts by numerically calculating accurate reference potentials for v T and the effective embedding potential for arbitrary systems, which allows for a spatially resolved comparison to approximate potentials.…”

Section: ͑1͒mentioning

confidence: 99%

Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds

Fux

Jacob

Neugebauer

et al. 2010

The Journal of Chemical Physics

197

278

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Dispersion, static correlation, and delocalisation errors in density functional theory: An electrostatic theorem perspective J. Chem. Phys. 135, 164110 (2011) Evaluation of coupling terms between intra-and intermolecular vibrations in coarse-grained normal-mode analysis: Does a stronger acid make a stiffer hydrogen bond? J. Chem. Phys. 135, 154111 (2011) Calculating dispersion interactions using maximally localized Wannier functions J. Chem. Phys. 135, 154105 (2011) A theoretical study of Ne3 using hyperspherical coordinates and a slow variable discretization approach J. Chem. Phys. 135, 134312 (2011) Additional information on J. Chem. Phys. The frozen-density embedding ͑FDE͒ scheme ͓Wesolowski and Warshel, J. Phys. Chem. 97, 8050 ͑1993͔͒ relies on the use of approximations for the kinetic-energy component v T ͓ 1 , 2 ͔ of the embedding potential. While with approximations derived from generalized-gradient approximation kinetic-energy density functional weak interactions between subsystems such as hydrogen bonds can be described rather accurately, these approximations break down for bonds with a covalent character. Thus, to be able to directly apply the FDE scheme to subsystems connected by covalent bonds, improved approximations to v T are needed. As a first step toward this goal, we have implemented a method for the numerical calculation of accurate references for v T . We present accurate embedding potentials for a selected set of model systems, in which the subsystems are connected by hydrogen bonds of various strength ͑water dimer and F-H-F − ͒, a coordination bond ͑ammonia borane͒, and a prototypical covalent bond ͑ethane͒. These accurate potentials are analyzed and compared to those obtained from popular kinetic-energy density functionals.

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“…But this argument holds only if one wishes to obtain the exact density of a given excited state. The analytically solvable model systems 33 provide examples of series of potentials v, which yield a series of the corresponding densities ρ approaching arbitrarily closely a target density which is not v-representable. The second reason is more related to the computational practice.…”

Section: Discussionmentioning

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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Orbital-Free Embedding Effective Potential in Analytically Solvable Cases

Cited by 17 publications

References 37 publications

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds

Embedding potentials for excited states of embedded species

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