TY - JOUR

T1 - Chemical bonding motifs from a tiling of the many-electron wavefunction

AU - Liu, Yu

AU - Frankcombe, Terry J.

AU - Schmidt, Timothy W.

N1 - Publisher Copyright:
© the Owner Societies 2016.

PY - 2016

Y1 - 2016

N2 - 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 Ψ2, 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.

AB - 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 Ψ2, 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.

UR - http://www.scopus.com/inward/record.url?scp=84971246209&partnerID=8YFLogxK

U2 - 10.1039/c6cp01188h

DO - 10.1039/c6cp01188h

M3 - Article

SN - 1463-9076

VL - 18

SP - 13385

EP - 13394

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 19

ER -