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Erschienen in:
Accurate Thermochemistry for Large Molecules with Modern Density Functionals Kapitel lesen Erstes Kapitel lesen

2015 | OriginalPaper | Buchkapitel

Non-analytic Spin-Density Functionals

verfasst von : Martín A. Mosquera, Adam Wasserman

Erschienen in: Density Functionals

Verlag: Springer International Publishing

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Abstract

We examine the integer discontinuity (or derivative discontinuity) of the exact energy functionals of Kohn–Sham density-functional theory for the spin-polarized case. The integer discontinuity and its cause, the piecewise linearity of the energy in the grand canonical ensemble, are required to improve the predictive power of density-functional approximations to the exchange-correlation energy. We show how any spin-polarized DFA can be adapted to display the proper integer discontinuity. The formalism we present here can be used to improve functionals further within spin density-functional theory and fragment-based formulations of DFT.

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Vorheriges Kapitel The Ring and Exchange-Ring Approximations Based on Kohn–Sham Reference States
Nächstes Kapitel Fractional Kohn–Sham Occupancies from a Strong-Correlation Density Functional
Anhänge
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Fußnoten
1
In this work by “subdensity-matrix” we mean a density matrix corresponding to a state with strictly an integer number of electrons.
 
2
The described ensemble is not a truly zero-temperature system because the spin-interactions are neglected.
 
3
Here we use Hund’s rules as a guide. Exceptions to these rules are known [39].
 
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Metadaten
Titel
Non-analytic Spin-Density Functionals
verfasst von
Martín A. Mosquera
Adam Wasserman
Copyright-Jahr
2015
Buch
Density Functionals

Print ISBN: 978-3-319-19691-6

Electronic ISBN: 978-3-319-19692-3

Copyright-Jahr: 2015

DOI
https://doi.org/10.1007/128_2014_619