DOI: 10.1063/1.478648. The importance of self-interaction and nonlocal exchange corrections to the density functional theory of intracavity electrons in Na-doped sodalites

The importance of self-interaction and nonlocal exchange corrections to the density functional theory of intracavity electrons in Na-doped sodalites

10.1063/1.478648

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Electrons that are confined to zeolite cavities are modeled using a simplified pseudopotential scheme to represent the interaction of the electrons with both the sodalite framework and the Na+ ions. By comparing theory with recent experimental studies of G centers in Na-doped NaBr-SOD it is demonstrated that restricted forms of density functional theory, where two electrons are forced to pair in the same Kohn–Sham orbital, fail to correctly predict the true nature of the singlet, (spin unpolarized), G center. Electron confinement leads to generalized gradient corrections to the exchange of 0.74 eV and self-interaction corrections (SIC) of 0.7 eV over calculations performed in the local spin density approximation (LSDA). Only the self-interaction corrected generalized gradient approximation and the unrestricted Hartree–Fock approximation are in accord with experiment for the relative stability of the triplet (spin polarized) state. The unrestricted Hartree–Fock method is used to show that G-center absorptions will be blueshifted with respect to absorptions due to the isolated F centers. Constructing a Hubbard Hamiltonian we show that the exchange coupling ranges in values from 2.3 meV(UHF) to 3.6 meV(SIC-LSDA) corresponding to Neel temperatures that range from 27 to 41 K in agreement with experiment.

Bibliography

Blake, N. P., & Metiu, H. (1999). The importance of self-interaction and nonlocal exchange corrections to the density functional theory of intracavity electrons in Na-doped sodalites. The Journal of Chemical Physics, 110(15), 7457â7466.

Authors 2

Nick P. Blake (first)
Horia Metiu (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:17 a.m.)
Deposited	1 year, 6 months ago (Feb. 7, 2024, 2:11 p.m.)
Indexed	1 year, 6 months ago (Feb. 7, 2024, 2:40 p.m.)
Issued	26 years, 4 months ago (April 15, 1999)
Published	26 years, 4 months ago (April 15, 1999)
Published Print	26 years, 4 months ago (April 15, 1999)

Funders 0

None

BibTeX

@article{Blake_1999, title={The importance of self-interaction and nonlocal exchange corrections to the density functional theory of intracavity electrons in Na-doped sodalites}, volume={110}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.478648}, DOI={10.1063/1.478648}, number={15}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Blake, Nick P. and Metiu, Horia}, year={1999}, month=apr, pages={7457–7466} }

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