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The influence of the exchange-correlation functional on the non-interacting kinetic energy and its implications for orbital-free density functional approximations

Kati Finzel (UGent) and Patrick Bultinck (UGent)
(2018) ACTA PHYSICO-CHIMICA SINICA. 34(6). p.650-655
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Abstract
In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other. This aspect is first derived in an orbital-free context. It is shown that the total Fermi potential depends on the density only, the individual parts, the Pauli kinetic energy and the exchange-correlation energy, however, are orbital dependent and as such mutually influence each other. The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy. The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the order of a few Hartrees. For chemical purposes, however, the energetic performance as a function of the nuclear coordinates is much more important than total energies. Therefore, the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide. The data reveals that, the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances. Therefore, the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy.
Keywords
GENERALIZED GRADIENT APPROXIMATION, ATOMIC SHELL STRUCTURE, ELECTRON-DENSITY, GROUND-STATE, KOHN-SHAM, QUANTUM CORRECTIONS, COULOMB-SYSTEMS, WAVE-FUNCTIONS, SQUARE-ROOT, FREE DFT, Density functional approximation, Density functional approximation, Kinetic energy functional, Exchange-correlation functional, Bond, dissociation energy, Bond distance

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Citation

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Chicago
Finzel, Kati, and Patrick Bultinck. 2018. “The Influence of the Exchange-correlation Functional on the Non-interacting Kinetic Energy and Its Implications for Orbital-free Density Functional Approximations.” Acta Physico-chimica Sinica 34 (6): 650–655.
APA
Finzel, K., & Bultinck, P. (2018). The influence of the exchange-correlation functional on the non-interacting kinetic energy and its implications for orbital-free density functional approximations. ACTA PHYSICO-CHIMICA SINICA, 34(6), 650–655.
Vancouver
1.
Finzel K, Bultinck P. The influence of the exchange-correlation functional on the non-interacting kinetic energy and its implications for orbital-free density functional approximations. ACTA PHYSICO-CHIMICA SINICA. 2018;34(6):650–5.
MLA
Finzel, Kati, and Patrick Bultinck. “The Influence of the Exchange-correlation Functional on the Non-interacting Kinetic Energy and Its Implications for Orbital-free Density Functional Approximations.” ACTA PHYSICO-CHIMICA SINICA 34.6 (2018): 650–655. Print.
@article{8559392,
  abstract     = {In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other. This aspect is first derived in an orbital-free context. It is shown that the total Fermi potential depends on the density only, the individual parts, the Pauli kinetic energy and the exchange-correlation energy, however, are orbital dependent and as such mutually influence each other. The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy. The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the order of a few Hartrees. For chemical purposes, however, the energetic performance as a function of the nuclear coordinates is much more important than total energies. Therefore, the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide. The data reveals that, the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances. Therefore, the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy.},
  author       = {Finzel, Kati and Bultinck, Patrick},
  issn         = {1000-6818},
  journal      = {ACTA PHYSICO-CHIMICA SINICA},
  keyword      = {GENERALIZED GRADIENT APPROXIMATION,ATOMIC SHELL STRUCTURE,ELECTRON-DENSITY,GROUND-STATE,KOHN-SHAM,QUANTUM CORRECTIONS,COULOMB-SYSTEMS,WAVE-FUNCTIONS,SQUARE-ROOT,FREE DFT,Density functional approximation,Density functional approximation,Kinetic energy functional,Exchange-correlation functional,Bond,dissociation energy,Bond distance},
  language     = {eng},
  number       = {6},
  pages        = {650--655},
  title        = {The influence of the exchange-correlation functional on the non-interacting kinetic energy and its implications for orbital-free density functional approximations},
  url          = {http://dx.doi.org/10.3866/PKU.WHXB201710251},
  volume       = {34},
  year         = {2018},
}

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