Investigation of exchange potentials for excited states by parameter fitting

Paragi, Gábor; Gyémánt, I.; Doren, V. E. Van

doi:10.1016/s0009-2614(00)00613-8

Cited by 9 publications

(8 citation statements)

References 10 publications

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“…The GOK principle provided a basis 062501-1 1050-2947/2013/87(6)/062501 (11) ©2013 American Physical Society for the ensemble DFT method [7,8] and its variants which employ the optimized effective potential (exchange only) [9][10][11]. Despite the substantial theoretical investigations of the ensemble variational theories, the practical implementations of the method have been rather scarce and limited to the calculation of excitation energies of atoms and small molecules at equilibrium geometries [12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

2013

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Section: Introductionmentioning

confidence: 99%

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

2013

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“…(24) and (26)] of calculating excitation energies. The results collected in Table II show that for the considered ensembles the quality of excitation energies does not heavily depend on the choice between formulae (24) and (26). The eLSDA-SIC excitation energies are improved with respect to the uncorrected eLSDA ones and a mean error drops from 0.…”

Section: Performance Of the Corrected Functionalsmentioning

confidence: 87%

“…(24) is more appropriate in calculation of excitation energies than that of Eq. (26). It is also possible to calculate a first excitation energy from orbital energies resulting from an ensemble calculation 14 but we did not explore this method as it is the least universal of the three mentioned methods.…”

Section: Performance Of the Corrected Functionalsmentioning

confidence: 99%

“…11 and 12. Substantial theoretical investigation of the ensemble DFT 7,8,10,[13][14][15][16][17][18][19] has not been paralleled by its practical implementations and the amount of numerical examples is rather scarce. Initial attempts of computing excitation energies have been mainly limited to atoms and small molecules and they involved using either local and semi-local functionals, [20][21][22][23][24][25][26][27] or the exact-exchange functional. 15,28,29 Calculations have been carried out via the Kohn-Sham (KS) scheme and, in case of the exact exchange functional, optimal effective potential (OEP) methods have been developed.…”

Section: Introductionmentioning

confidence: 99%

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Ensemble density variational methods with self- and ghost-interaction-corrected functionals

Pastorczak

Pernal

2014

The Journal of Chemical Physics

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Articles you may be interested in Spin-flip, tensor equation-of-motion configuration interaction with a density-functional correction: A spin-complete method for exploring excited-state potential energy surfaces J. Chem. Phys. 143, 234107 (2015) (2001)] (the acronym eDFT proposed in analogy to eHF -ensemble Hartree-Fock method). Local and semi-local ground-state density functionals are employed in both approaches. Approximate ensemble density functionals contain not only spurious self-interaction but also the so-called ghost-interaction which has no counterpart in the ground-state DFT. We propose how to correct the GOK functional for both kinds of interactions in approximations that go beyond the exact-exchange functional. Numerical applications lead to a conclusion that functionals free of the ghost-interaction by construction, i.e., eDFT, yield much more reliable results than approximate self-and ghost-interaction-corrected GOK functional. Additionally, local density functional corrected for self-interaction employed in the eDFT framework yields excitations energies of the accuracy comparable to that of the uncorrected semi-local eDFT functional. © 2014 AIP Publishing LLC. [http://dx

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“…Pastorczak et al [21] have recently shown that the Helmholtz free-energy variational principle can be connected to the GOK variational principle. Despite the substantial theoretical investigations of ensemble DFT for excited states, GOK-DFT has been applied only to the calculation of excitation energies in atoms and small molecules [22][23][24][25]. One of the reason for the lack of success of GOK-DFT is the absence of appropriate exchange-correlation functionals for ensembles.…”

Section: Introductionmentioning

confidence: 99%

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H₂ molecule

Franck

Fromager

2013

Molecular Physics

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A generalized adiabatic connection for ensembles (GACE) is presented. In contrast to the traditional adiabatic connection formulation, both ensemble weights and interaction strength can vary along a GACE path while the ensemble density is held fixed. The theory is presented for non-degenerate two-state ensembles but it can in principle be extended to any ensemble of fractionally occupied excited states. Within such a formalism an exact expression for the ensemble exchange-correlation density-functional energy, in terms of the conventional ground-state exchange-correlation energy, is obtained by integration over the ensemble weight. Stringent constraints on the functional are thus obtained when expanding the ensemble exchange-correlation energy through second order in the ensemble weight. For illustration purposes, the analytical derivation of the GACE is presented for the H 2 model system in a minimal basis, leading thus to a simple density-functional approximation to the ensemble exchange-correlation energy. Encouraging results were obtained with this approximation for the description in a large basis of the first 1 Σ + g excitation in H 2 upon bond stretching. Finally, a range-dependent GACE has been derived, providing thus a pathway to the development of a rigorous state-average multi-determinant density-functional theory.

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Investigation of exchange potentials for excited states by parameter fitting

Cited by 9 publications

References 10 publications

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

Ensemble density variational methods with self- and ghost-interaction-corrected functionals

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H₂ molecule

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Investigation of exchange potentials for excited states by parameter fitting

Cited by 9 publications

References 10 publications

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle

Ensemble density variational methods with self- and ghost-interaction-corrected functionals

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H2 molecule

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Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H₂ molecule