The electronic structure of benzene from a tiling of the correlated 126-dimensional wavefunction.

Nature Communications
Yu LiuTimothy W Schmidt

Abstract

The electronic structure of benzene is a battleground for competing viewpoints of electronic structure, with valence bond theory localising electrons within superimposed resonance structures, and molecular orbital theory describing delocalised electrons. But, the interpretation of electronic structure in terms of orbitals ignores that the wavefunction is anti-symmetric upon interchange of like-spins. Furthermore, molecular orbitals do not provide an intuitive description of electron correlation. Here we show that the 126-dimensional electronic wavefunction of benzene can be partitioned into tiles related by permutation of like-spins. Employing correlated wavefunctions, these tiles are projected onto the three dimensions of each electron to reveal the superposition of Kekulé structures. But, opposing spins favour the occupancy of alternate Kekulé structures. This result succinctly describes the principal effect of electron correlation in benzene and underlines that electrons will not be spatially paired when it is energetically advantageous to avoid one another.

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Aug 9, 2019·Chemical Science·Yu LiuTimothy W Schmidt
Jan 10, 2020·The Journal of Physical Chemistry Letters·Yu LiuTimothy W Schmidt

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Citations

Sep 29, 2020·Nature Communications
Nov 8, 2020·Physical Chemistry Chemical Physics : PCCP·Leonard Reuter, Arne Lüchow
Nov 4, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Josep M Oliva-EnrichJosé Elguero
Aug 12, 2021·Nature Communications·Leonard Reuter, Arne Lüchow
Dec 29, 2020·The Journal of Physical Chemistry Letters·Janus J Eriksen
Oct 7, 2020·The Journal of Physical Chemistry Letters·Janus J EriksenJürgen Gauss

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