Excitation energies from frozen-density embedding with accurate embedding potentials

Artiukhin, Denis G.; Jacob, Christoph R.; Neugebauer, Johannes

doi:10.1063/1.4922429

Cited by 27 publications

(35 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The embedding potential results in an additional one-electron term in the Hamiltonian. Alternatively, a fixed (i.e., ρ A -independent) embedding potential can be derived by the inversion technique [25][26][27][28][29][30] leading to similar advantages. Using a fixed embedding potential leads, however, to the inconsistency between the energy and embedded wave function.…”

Section: Introductionmentioning

confidence: 99%

Orthogonality of embedded wave functions for different states in frozen-density embedding theory

Zech

Aquilante

Wesołowski

2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

Other than lowest-energy stationary embedded wave functions obtained in Frozen-Density Embedding Theory (FDET) [T. A. Wesolowski, Phys. Rev. A 77, 012504 (2008)] can be associated with electronic excited states but they can be mutually non-orthogonal. Although this does not violate any physical principles -embedded wave functions are only auxiliary objects used to obtain stationary densities -working with orthogonal functions has many practical advantages. In the present work, we show numerically that excitation energies obtained using conventional FDET calculations (allowing for non-orthogonality) can be obtained using embedded wave functions which are strictly orthogonal. The used method preserves the mathematical structure of FDET and self-consistency between energy, embedded wave function, and the embedding potential (they are connected through the Euler-Lagrange equations). The orthogonality is built-in through the linearization in the embedded density of the relevant components of the total energy functional. Moreover, we show formally that the differences between the expectation values of the embedded Hamiltonian are equal to the excitation energies, which is the exact result within linearized FDET. Linearized FDET is shown to be a robust approximation for a large class of reference densities. C 2015 AIP Publishing LLC. [http://dx

show abstract

Section: Introductionmentioning

confidence: 99%

Orthogonality of embedded wave functions for different states in frozen-density embedding theory

Zech

Aquilante

Wesołowski

2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Artiukhin et al applied the inversion procedure by Fux et al in calculations of excitation energies obtained from the method combining FDET and LR‐TDDFT for several organic chromophores such as cis ‐hydroxyquinoline, 2‐aminopyridine, acetophenone, in complex with small hydrogen bonded such as water or methanol. For numerical inversion, the improved procedure introduced by Jacob was used.…”

Section: Nonadditive Kinetic Potential From Inversion Proceduresmentioning

confidence: 99%

“…In either cases, the analytical form of the functional derivative is known and can be used in Equation 15 to approximate v nad 0 t ½q A ; q B ðrÞ.…”

Section: Numerical Inversion Of the Kohn-sham Equation With Finitementioning

confidence: 99%

“…Other authors used accurate inverted potentials to detect flaws of explicit approximations to

v_{t}^{nad} [ρ_{A}, ρ_{tot}] (r)

and to determine their limits of applicability . Inverted potentials are key elements of various simulation methods . Such studies provide frequently direct or indirect (through calculated observables) information about the quality of the inverted nonadditive kinetic potential.…”

Section: Introductionmentioning

confidence: 99%

“…[4][5][6][7] Inverted potentials are key elements of various simulation methods. [3,[8][9][10][11][12][13][14][15][16] Such studies provide frequently direct or indirect (through calculated observables) information about the quality of the inverted nonadditive kinetic potential.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Nonadditive kinetic potentials from inverted Kohn–Sham problem

Banafsheh¹,

Wesołowski²

2017

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The nonadditive kinetic potential is a key element in density-dependent embedding methods. The correspondence between the ground-state density and the total effective Kohn-Sham potential provides the basis for various methods to construct the nonadditive kinetic potential for any pair of electron densities. Several research groups used numerical or analytical inversion procedures to explore this strategy which overcomes the failures of known explicit density functional approximations. The numerical inversions, however, apply additional approximations/simplifications. The relations known for the exact quantities cannot be assumed to hold for quantities obtained in numerical inversions. The exact relations are discussed with special emphasis on such issues as: the admissibility of the densities for which the potential is constructed, the choice of densities to be used as independent variables, self-consistency between the potentials and observables calculated using the embedded wavefunction, and so forth. The review focuses on how these issues are treated in practice. The review is supplemented with the analysis of the inverted potentials for weakly overlapping pairs of electron densities-the case not studied previously.density embedding, density functional theory, electron density overlap | I N TR ODU C TI ONThe nonadditive kinetic energy (T nad s ) and potential (v nad t ðrÞ) are key ingredients in numerical simulation methods exploring the density embedding strategy (see section 1.2). Both quantities are defined as functionals of admissible pairs of electron densities: where W s denotes a N-electron single-determinant trial wavefunction. Atomic units are used throughout this work.In practical applications, q A ðrÞ is the density corresponding to the wavefunction W emb associated with the embedded subsystem and q tot ðrÞ is electron density of the total system comprising the part represented by W emb and its "environment." Usually, explicit density functionals approximate the functionals v nad t ½q A ; q tot ðrÞ and/or T nad s ½q A ; q tot . Simulations and studies on model systems reported by several researchers revealed many cases where the currently known explicit density functionals fail (see section 1.2). These failures resulted in recent interest in an alternative -implicit -strategy to construct v nad t ½q A ; q tot ðrÞ (and T nad s ½q A ; q tot ) for arbitrarily chosen pairs of densities q A ðrÞ and q tot ðrÞ. Such constructions are based on the Levy correspondence [1] between the Kohn-Sham potential [2] and the electron density. This correspondence exists for admissible electron Int J Quantum Chem. 2018;118:e25410.

show abstract

Polarization Energies from Efficient Representation of the Linear Density–Density Response Function

Dreßler

Sebastiani

2021

Advcd Theory and Sims

View full text Add to dashboard Cite

The authors present a proof‐of‐concept study for the calculation of atomic forces on a solvated molecule by means of the linear density–density response function in its moment expanded representation. The density–density response function represents an efficient way to compute molecular forces for arbitrary external potentials via an ab initio scheme, without the need to perform an explicit self‐consistent quantum chemical calculation for each configuration of the chemical environment. Here, the authors show that it is indeed possible to determine the atomic forces of interacting bulk‐like molecular complexes due to polarization effects of the surrounding molecules with good accuracy. This study represents a significant step the practical applicability of the approach, which is still in a development phase. The potential application of the computational scheme in terms of molecular dynamics simulations is illustrated by considering a variety of cluster conformations, as they would be found within a molecular dynamics trajectory.

show abstract

Excitation energies from frozen-density embedding with accurate embedding potentials

Cited by 27 publications

References 47 publications

Orthogonality of embedded wave functions for different states in frozen-density embedding theory

Orthogonality of embedded wave functions for different states in frozen-density embedding theory

Nonadditive kinetic potentials from inverted Kohn–Sham problem

Polarization Energies from Efficient Representation of the Linear Density–Density Response Function

Contact Info

Product

Resources

About