Concerning the applicability of density functional methods to atomic and molecular negative ions

Galbraith, John Morrison; Schaefer, Henry F.

doi:10.1063/1.471933

Cited by 206 publications

(165 citation statements)

References 21 publications

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“…30,50 For the atomic systems, the MAD are 0.130 eV ͑PBE͒, 0.071 ͑revPBE͒, 0.119 ͑B86PBE͒, and 0.081 ͑xPBE͒. All four functionals perform significantly better for the second low atoms.…”

Section: Ionization Potentials Electron Affinities and Proton Afmentioning

confidence: 99%

“…[47][48][49][50] On one hand, the ''self-interaction error'' causes the Kohn-Sham orbital energies to be shifted upwards artificially, leading to positive ͑unstable͒ orbital energies for the highest occupied orbitals of an anion. On the other hand, an artificial stabilization is provided by employing a finite basis sets with functions localized at the anion.…”

Section: Ionization Potentials Electron Affinities and Proton Afmentioning

confidence: 99%

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The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems

Goddard

2004

The Journal of Chemical Physics

161

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Density functional theory ͑DFT͒ has become the method of choice for many applications of quantum mechanics to the study of the electronic properties of molecules and solids. Despite the enormous progress in improving the functionals, the current generation is inadequate for many important applications. As part of the quest of finding better functionals, we consider in this paper the Perdew-Burke-Ernzerhof ͑PBE͒ functional, which we believe to have the best theoretical foundation, but which leads to unacceptable errors in predicting thermochemical data ͑heats of formation͒ of molecular systems ͓mean absolute deviation ͑MAD͒ϭ16.9 kcal/mol against the extended G2 data set of 148 molecules͔. Much improved thermochemistry is obtained with hybrid DFT methods that include part of the Hartree-Fock exchange ͓thus B3LYP ͑Becke's three parameter scheme combining Hartree-Fock exchange, Becke gradient corrected exchange functional and Lee-Yang-Parr correlational functional͒ with MADϭ3.1 kcal/mol and PBE0 ͑Perdew's hybrid scheme using PBE exchange and correlation functionals͒ with MADϭ4.8 kcal/mol͔. However we wish to continue the quest for a pure density-based DFT. Thus we optimized the four free parameters ͑ , , ␣, and ␤͒ in PBE theory against experimental atomic data and the van der Waals interaction properties of Ne 2 , leading to the xPBE extended functional, which significantly outperforms PBE for thermochemical properties MAD reduced to 8.0 kcal/mol while being competitive or better than PBE for predictions of geometric parameters, ionization potentials, electron affinities, and proton affinities and for the description of van der Waals and hydrogen bond interactions. Thus xPBE significantly enlarges the field of applications available for pure DFT. The functional forms thus obtained for the exchange and correlational functionals may be useful for discovering new improved functionals or formalisms.

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Section: Ionization Potentials Electron Affinities and Proton Afmentioning

confidence: 99%

Section: Ionization Potentials Electron Affinities and Proton Afmentioning

confidence: 99%

The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems

Goddard

2004

The Journal of Chemical Physics

161

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“…Unfortunately, for the atoms and very small molecules studied here, it is well-known [110][111][112] that with common semi-local approximations negative ions of small systems may erroneously be predicted to be unstable. However, when performing calculations with finite basis sets, as in, e.g., [113], unbound states can be artificially stabilized [114], because the basis set effectively confines the unbound electron to the vicinity of the neutral system. Because the ensemble generalization discussed here does not change the total energies of systems with integer electrons (including neutrals, cations, and anions), anions that are not bound with the underlying xc functional will remain unbound even if its ensemble-generalized version is employed.…”

Section: B Evaluating the Test Set -A Systematic Studymentioning

confidence: 99%

Effect of ensemble generalization on the highest-occupied Kohn-Sham eigenvalue

Kraisler

Schmidt

Kümmel

et al. 2015

The Journal of Chemical Physics

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There are several approximations to the exchange-correlation functional in density-functional theory that accurately predict total energy-related properties of many-electron systems, such as binding energies, bond lengths, and crystal structures. Other approximations are designed to describe potential-related processes, such as charge transfer and photoemission. However, the development of a functional which can serve the two purposes simultaneously is a long-standing challenge. Trying to address it, we employ in the current work the ensemble generalization procedure proposed in Phys. Rev. Lett. 110, 126403 (2013). Focusing on the prediction of the ionization potential via the highest occupied Kohn-Sham eigenvalue, we examine a variety of exchange-correlation approximations: the local spin-density approximation, semi-local generalized gradient approximations, and global and local hybrid functionals. Results for a test set of 26 diatomic molecules and single atoms are presented. We find that the aforementioned ensemble generalization systematically improves the prediction of the ionization potential, for various systems and exchange-correlation functionals, without compromising the accuracy of total energy-related properties. We specifically examine hybrid functionals. These depend on a parameter controlling the ratio of semi-local to non-local functional components. The ionization potential obtained with ensemble-generalized functionals is found to depend only weakly on the parameter value, contrary to common experience with non-generalized hybrids, thus eliminating one aspect of the so-called 'parameter dilemma' of hybrid functionals.

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“…ÅÀ were optimized at the B3LYP/ DZP++ level of theory [14][15][16][17] using GAMESS-UK [21]. As noted previously in the linear acene series [14], application of the DZP++ basis set has one major drawback.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Unfortunately, experimental AEAs of CP-PAHs are not available [8]. Therefore, we were prompted to compute AEAs of a representative series of (CP)-PAHs at the ab initio B3LYP/DZP++ level of theory [14][15][16][17]. We here report and discuss the gas phase AEAs with and without zero-point vibrational energy (ZPVE) [9,10] and the bowl-shaped corannulene (9) [19,20] (Fig.…”

Section: Introductionmentioning

confidence: 99%

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

Todorov

Koper

Lenthe

et al. 2008

Chemical Physics Letters

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The B3LYP/DZP++ adiabatic electron affinity (AEA) of nine (non)-alternant polycyclic aromatic hydrocarbons are reported and discussed. Calculations became feasible for molecules this size by projecting out the near-linearly dependent part of the one-electron basis. Non-alternant PAH consisting of an alternant PAH core modified by peri-annulation with unsaturated five-membered rings (CP-PAHs) possess markedly enhanced AEAs.

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Concerning the applicability of density functional methods to atomic and molecular negative ions

Cited by 206 publications

References 21 publications

The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems

The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems

Effect of ensemble generalization on the highest-occupied Kohn-Sham eigenvalue

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

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