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On the evaluation of the non-interacting kinetic energy in density functional theory

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On the evaluation of the non-interacting kinetic energy in density functional theory. / Peach, Michael J. G.; Griffiths, David G. J.; Tozer, David J.
In: Journal of Chemical Physics, Vol. 136, No. 14, ARTN 144101, 14.04.2012.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Harvard

Peach, MJG, Griffiths, DGJ & Tozer, DJ 2012, 'On the evaluation of the non-interacting kinetic energy in density functional theory', Journal of Chemical Physics, vol. 136, no. 14, ARTN 144101. https://doi.org/10.1063/1.3700436

APA

Peach, M. J. G., Griffiths, D. G. J., & Tozer, D. J. (2012). On the evaluation of the non-interacting kinetic energy in density functional theory. Journal of Chemical Physics, 136(14), Article ARTN 144101. https://doi.org/10.1063/1.3700436

Vancouver

Peach MJG, Griffiths DGJ, Tozer DJ. On the evaluation of the non-interacting kinetic energy in density functional theory. Journal of Chemical Physics. 2012 Apr 14;136(14):ARTN 144101. doi: 10.1063/1.3700436

Author

Peach, Michael J. G. ; Griffiths, David G. J. ; Tozer, David J. / On the evaluation of the non-interacting kinetic energy in density functional theory. In: Journal of Chemical Physics. 2012 ; Vol. 136, No. 14.

Bibtex

@article{664ae6e87ed649f19739b35cef0fa6ba,
title = "On the evaluation of the non-interacting kinetic energy in density functional theory",
abstract = "The utility of both an orbital-free and a single-orbital expression for computing the non-interacting kinetic energy in density functional theory is investigated for simple atomic systems. The accuracy of both expressions is governed by the extent to which the Kohn-Sham equation is solved for the given exchange-correlation functional and so special attention is paid to the influence of finite Gaussian basis sets. The orbital-free expression is a statement of the virial theorem and its accuracy is quantified. The accuracy of the single-orbital expression is sensitive to the choice of Kohn-Sham orbital. The use of particularly compact orbitals is problematic because the failure to solve the Kohn-Sham equation exactly in regions where the orbital has decayed to near-zero leads to unphysical behaviour in regions that contribute to the kinetic energy, rendering it inaccurate. This problem is particularly severe for core orbitals, which would otherwise appear attractive due to their formally nodeless nature. The most accurate results from the single-orbital expression are obtained using the relatively diffuse, highest occupied orbitals, although special care is required at orbital nodes. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3700436]",
keywords = "ORBITALS, ATOMIC IONS, ELECTRON-DENSITIES, STATE CORRELATION ENERGIES",
author = "Peach, {Michael J. G.} and Griffiths, {David G. J.} and Tozer, {David J.}",
year = "2012",
month = apr,
day = "14",
doi = "10.1063/1.3700436",
language = "English",
volume = "136",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "AMER INST PHYSICS",
number = "14",

}

RIS

TY - JOUR

T1 - On the evaluation of the non-interacting kinetic energy in density functional theory

AU - Peach, Michael J. G.

AU - Griffiths, David G. J.

AU - Tozer, David J.

PY - 2012/4/14

Y1 - 2012/4/14

N2 - The utility of both an orbital-free and a single-orbital expression for computing the non-interacting kinetic energy in density functional theory is investigated for simple atomic systems. The accuracy of both expressions is governed by the extent to which the Kohn-Sham equation is solved for the given exchange-correlation functional and so special attention is paid to the influence of finite Gaussian basis sets. The orbital-free expression is a statement of the virial theorem and its accuracy is quantified. The accuracy of the single-orbital expression is sensitive to the choice of Kohn-Sham orbital. The use of particularly compact orbitals is problematic because the failure to solve the Kohn-Sham equation exactly in regions where the orbital has decayed to near-zero leads to unphysical behaviour in regions that contribute to the kinetic energy, rendering it inaccurate. This problem is particularly severe for core orbitals, which would otherwise appear attractive due to their formally nodeless nature. The most accurate results from the single-orbital expression are obtained using the relatively diffuse, highest occupied orbitals, although special care is required at orbital nodes. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3700436]

AB - The utility of both an orbital-free and a single-orbital expression for computing the non-interacting kinetic energy in density functional theory is investigated for simple atomic systems. The accuracy of both expressions is governed by the extent to which the Kohn-Sham equation is solved for the given exchange-correlation functional and so special attention is paid to the influence of finite Gaussian basis sets. The orbital-free expression is a statement of the virial theorem and its accuracy is quantified. The accuracy of the single-orbital expression is sensitive to the choice of Kohn-Sham orbital. The use of particularly compact orbitals is problematic because the failure to solve the Kohn-Sham equation exactly in regions where the orbital has decayed to near-zero leads to unphysical behaviour in regions that contribute to the kinetic energy, rendering it inaccurate. This problem is particularly severe for core orbitals, which would otherwise appear attractive due to their formally nodeless nature. The most accurate results from the single-orbital expression are obtained using the relatively diffuse, highest occupied orbitals, although special care is required at orbital nodes. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3700436]

KW - ORBITALS

KW - ATOMIC IONS

KW - ELECTRON-DENSITIES

KW - STATE CORRELATION ENERGIES

UR - http://www.scopus.com/inward/record.url?scp=84859995931&partnerID=8YFLogxK

U2 - 10.1063/1.3700436

DO - 10.1063/1.3700436

M3 - Journal article

VL - 136

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 14

M1 - ARTN 144101

ER -