Exchange-Correlation Energy Densities and Response Potentials: Connection Between Two Definitions and Analytical Model for the Strong-Coupling Limit of a Stretched Bond

Giarrusso, S.; Gori‐Giorgi, Paola

doi:10.26434/chemrxiv.10283678

Cited by 2 publications

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“…Static correlation is well-known to be a difficult regime for density functional approximations in the ground state, and its implication for excitation energies and response are very challenging; some recent progress based on the strictly-correlated electron approach for dissociation can be found in Refs. (133,134,135).…”

Section: Charge-transfer Excitations Between Open-shell Fragmentsmentioning

confidence: 99%

Double and Charge-Transfer Excitations in Time-Dependent Density Functional Theory

Maitra¹

2021

Preprint

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Time-dependent density functional theory has emerged as a method of choice for calculations of spectra and response properties in physics, chemistry, and biology, with its system-size scaling enabling computations on systems much larger than possible otherwise. While increasingly complex and interesting systems have been successfully tackled with relatively simple functional approximations, there has also been increasing awareness that these functionals tend to fail for certain classes of approximations. I review the fundamental challenges the approximate functionals have in describing double-excitations and charge-transfer excitations, which are two of the most common impediments for the theory to be applied in a black box way. At the same time, I describe the progress made in recent decades in developing functional approximations that give useful predictions for these excitations.

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Section: Charge-transfer Excitations Between Open-shell Fragmentsmentioning

confidence: 99%

Double and Charge-Transfer Excitations in Time-Dependent Density Functional Theory

Maitra¹

2021

Preprint

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“…This feature has received further interest in the literature. [11][12][13][14][15][16][17][18][19] In Ref. 4, it was demonstrated that such step structure (with height ∆I = I A − I B if A has higher ionization potential) is due to the response potential v resp .…”

Section: Introductionmentioning

confidence: 99%

Secondary kinetic peak in the Kohn-Sham potential and its connection to the response step

Giarrusso¹,

Neugarten²,

Baerends³

et al. 2022

Preprint

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We consider a prototypical 1D model Hamiltonian for a stretched heteronuclear molecule and construct individual components of the corresponding KS potential, namely: the kinetic, the N − 1, and the conditional potentials. These components show very special features, such as peaks and steps, in regions where the density is drastically low. Some of these features are quite well known, whereas others, such as a secondary peak in the kinetic potential or a second bump in the conditional potential, are less or not known at all. We discuss these features building on the analytical model treated in J. Chem. Theory Comput. 14, 4151 (2018). In particular, we provide an explanation for the underlying mechanism which determines the appearance of both peaks in the kinetic potential and elucidate why these peaks delineate the region over which the plateau structure, due to the N − 1 potential, stretches. We assess the validity of the Heitler-London Ansatz at large but finite internuclear distance, showing that, if optimal orbitals are used, this model is an excellent approximation to the exact wavefunction. Notably, we find that the second natural orbital presents an extra node very far out on the side of the more electronegative atom.

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Exchange-Correlation Energy Densities and Response Potentials: Connection Between Two Definitions and Analytical Model for the Strong-Coupling Limit of a Stretched Bond

Cited by 2 publications

References 0 publications

Double and Charge-Transfer Excitations in Time-Dependent Density Functional Theory

Double and Charge-Transfer Excitations in Time-Dependent Density Functional Theory

Secondary kinetic peak in the Kohn-Sham potential and its connection to the response step

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