Chemical bonding motifs from a tiling of the many-electron wavefunction.
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.
School of Chemistry, UNSW Sydney, NSW 2052, Australia. timothy.schmidt@unsw.edu.au.
Yu
Y
Liu
School of Physical Environmental and Mathematical Sciences, UNSW Canberra, ACT 2600, Australia.
Terry J
TJ
Frankcombe
School of Chemistry, UNSW Sydney, NSW 2052, Australia. timothy.schmidt@unsw.edu.au.
Timothy W
TW
Schmidt