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Issue 19, 2016
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Chemical bonding motifs from a tiling of the many-electron wavefunction

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Abstract

A method is presented to partition the 3N-dimensional space of a many-electron wavefunction into hyper-regions related by permutation symmetry. These hyper-regions represent unit cells, or “tiles” of the wavefunction from which the wavefunction may be regenerated in its entirety upon application of the set of permutations of like-spin electrons. The method, wherein a Voronoi diagram is constructed from the (even permutations of the) average position of a swarm of Monte Carlo walkers sampling |Ψ|2, determines a self-consistent partitioning of the wavefunction. When one of the identical 3N-dimensional Voronoi sites is projected onto the coordinates of each electron, chemical motifs naturally appear, such as core electrons, lone-pairs, single-bonds and banana-bonds. The structures determined for N2, O2, F2, and other molecules correspond to the double-quartet theory of Linnett. When the procedure is applied to C2, we arrive at an interpretation of its bonding in terms of a near triple bond with singlet-coupled outer electrons.

Graphical abstract: Chemical bonding motifs from a tiling of the many-electron wavefunction

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Article information


Submitted
22 Feb 2016
Accepted
20 Apr 2016
First published
21 Apr 2016

Phys. Chem. Chem. Phys., 2016,18, 13385-13394
Article type
Paper

Chemical bonding motifs from a tiling of the many-electron wavefunction

Y. Liu, T. J. Frankcombe and T. W. Schmidt, Phys. Chem. Chem. Phys., 2016, 18, 13385
DOI: 10.1039/C6CP01188H

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