Electron localization function
In quantum chemistry, the electron
localization function (ELF) is a measure of
the likelihood of finding an electron in the
neighborhood space of a reference electron
located at a given point and with the same spin.
Physically, this measures the extent of spatial
localization of the reference electron and
provides a method for the mapping of electron
pair probability in multielectronic systems.
ELF's usefulness stems from the observation
that it allows electron localization to be
analyzed in a chemically intuitive way. For
example, the shell structure of heavy atoms is
obvious when plotting ELF against the radial
Electron localization function of the krypton atom at the
distance from the nucleus; the ELF for radon
Hartree–Fock / cc-pV5Z level of theory. Also shown is the
has six clear maxima, whereas the electronic
density decreases monotonically and the radial density, 4πr2ρ(r), scaled by a factor of 0.0375.
radially weighted density fails to show all
shells. When applied to molecules, an analysis
of the ELF shows a clear separation between the core and valence electron, and also shows covalent bonds
and lone pairs, in what has been called "a faithful visualization of VSEPR theory in action".[1] Another
feature of the ELF is that it is invariant concerning the transformation of the molecular orbitals.
The ELF was originally defined by Becke and Edgecombe in
1990.[1] They first argued that a measure of the electron
localization is provided by
where ρ is the electron spin density and τ the kinetic energy
density. The second term (negative term) is the bosonic kinetic
energy density, so D is the contribution due to fermions. D is
expected to be small in those regions of space where localized
electrons are to be found. Given the arbitrariness of the
magnitude of the localization measure provided by D, it is
compared to the corresponding value for a uniform electron
Image of the ELF of water at level 0.8,
gas with spin density equal to ρ(r), which is given by
generated using PyMOL
The ratio,
is a dimensionless localization index that expresses electron localization for the uniform electron gas. In the
final step, the ELF is defined in terms of χ by mapping its values on to the range 0 ≤ ELF ≤ 1 by defining
the electron localization function as
ELF = 1 corresponding to perfect localization and ELF = ½ corresponding to the electron gas.
The original derivation was based on Hartree–Fock theory. For density functional theory, the approach was
generalized by Andreas Savin in 1992,[2] who also have applied the formulation to examining various
chemical and materials systems.[3] In 1994, Bernard Silvi and Andreas Savin developed a method for
explaining ELFs using differential topology.[4]
The approach of electron localization, in the form of atoms in molecules (AIM), was pioneered by Richard
Bader.[5] Bader's analysis partitions the charge density in a molecule to "atoms" according to zero-flux
surfaces (surfaces across which no electron flow is taking place).[6] Bader's analysis allows many properties
such as multipole moments, energies and forces, to be partitioned in a defensible and consistent manner to
individual atoms within molecules.
Both the Bader approach and the ELF approach to partitioning of molecular properties have gained
popularity in recent years because the fastest, accurate ab-initio calculations of molecular properties are now
mostly made using density functional theory (DFT), which directly calculates the electron density. This
electron density is then analyzed using the Bader charge analysis of Electron Localization Functions. One
of the most popular functionals in DFT was first proposed by Becke, who also originated Electron
Localization Functions.
References
1. A. D. Becke and K. E. Edgecombe (1990). "A simple measure of electron localization in
atomic and molecular systems". J. Chem. Phys. 92 (9): 5397–5403.
Bibcode:1990JChPh..92.5397B (https://ui.adsabs.harvard.edu/abs/1990JChPh..92.5397B).
doi:10.1063/1.458517 (https://doi.org/10.1063%2F1.458517).
2. Savin, A.; Jepsen, O.; Flad, J.; Andersen, O. K.; Preuss, H.; von Schnering, H. G. (1992).
"Electron localization in solid-state structures of the elements – the diamond structure".
Angewandte Chemie International Edition in English. 31 (2): 187–188.
doi:10.1002/anie.199201871 (https://doi.org/10.1002%2Fanie.199201871).
3. Savin, Andreas; Nesper, Reinhard; Wengert, Steffen; Fässler, Thomas F. (1997-09-17). "ELF:
The Electron Localization Function" (https://onlinelibrary.wiley.com/doi/10.1002/anie.199718
081). Angewandte Chemie International Edition in English. 36 (17): 1808–1832.
doi:10.1002/anie.199718081 (https://doi.org/10.1002%2Fanie.199718081). ISSN 0570-0833
(https://www.worldcat.org/issn/0570-0833).
4. Silvi, B.; Savin, A. (1994). "Classification of chemical bonds based on topological analysis of
electron localization functions" (http://www.nature.com/articles/371683a0). Nature. 371
(6499): 683–686. Bibcode:1994Natur.371..683S (https://ui.adsabs.harvard.edu/abs/1994Nat
ur.371..683S). doi:10.1038/371683a0 (https://doi.org/10.1038%2F371683a0). ISSN 0028-
0836 (https://www.worldcat.org/issn/0028-0836). S2CID 4362878 (https://api.semanticschola
r.org/CorpusID:4362878).
5. Bader, R. W. F. (1994). Atoms in Molecules: A Quantum Theory. Oxford University Press.
ISBN 978-0-19-855865-1.
6. Bader, Richard F. W. (2001-04-04). "The zero-flux surface and the topological and quantum
definitions of an atom in a molecule" (http://link.springer.com/10.1007/s002140000233).
Theoretical Chemistry Accounts: Theory, Computation, and Modeling. 105 (4–5): 276–283.
doi:10.1007/s002140000233 (https://doi.org/10.1007%2Fs002140000233). ISSN 1432-881X
(https://www.worldcat.org/issn/1432-881X). S2CID 120944734 (https://api.semanticscholar.or
g/CorpusID:120944734).
External links
Frank R. Wagner (ed.) Electron localizability: chemical bonding analysis in direct and
momentum space (http://www.cpfs.mpg.de/ELF/index.php). Max-Planck-Institut für
Chemische Physik fester Stoffe, 2002. (accessed 2008-09-02).
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