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English

Non-Additive Kinetic Energy and Potential in Analytically Solvable Systems and Their Approximated Counterparts

Published inWesolowski, Tomasz A. ; Wang, Yan Alexander (Ed.), Recent Progress in Orbital-free Density Functional Theory, p. 275-295
PublisherWorld Scientific
Collection
  • Recent Advances in Computational Chemistry; 6
Publication date2013
Abstract

The one-electron equation for orbitals embedded in frozen electron density (Eqs. 20-21 in [Wesolowski and Warshel, J. Phys. Chem, 97 (1993) 8050]) in its exact and approximated version is solved for an analytically solvable model system. The system is used to discuss the role of the embedding potential in preventing the collapse of a variationally obtained electron density onto the nucleus in the case when the frozen density is chosen to be that of the innermost shell. The approximated potential obtained from the second-order gradient expansion for the kinetic energy prevents such a collapse almost perfectly but this results from partial compensation of flaws of its components. It is also shown that that the quality of a semi-local approximation to the kinetic-energy functional, a quantity needed in orbital-free methods, is not related to the quality of the non-additive kinetic energy potential - a key component of the effective embedding potential in one-electron equations for embedded orbitals.

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Citation (ISO format)
WESOLOWSKI, Tomasz Adam, SAVIN, Andreas. Non-Additive Kinetic Energy and Potential in Analytically Solvable Systems and Their Approximated Counterparts. In: Recent Progress in Orbital-free Density Functional Theory. Wesolowski, Tomasz A. ; Wang, Yan Alexander (Ed.). [s.l.] : World Scientific, 2013. p. 275–295. (Recent Advances in Computational Chemistry) doi: 10.1142/9789814436731_0009
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Book chapter (Published version)
accessLevelPublic
Identifiers
ISBN978-981-4436-72-4
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Creation05/06/2013 14:48:00
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