Maxima of |Ψ|2: A connection between quantum mechanics and Lewis structures

The maxima of squared electronic wave functions |Ψ|2 are analyzed for a number of small molecules. They are in principle observables and show considerable chemical insight from first principles. The maxima contain substantial information about the relative electron positions in a molecule, such as t...

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Bibliographic Details
Published in:Journal of computational chemistry 2014-04, Vol.35 (11), p.854-864
Main Author: Lüchow, Arne
Format: Article
Language:English
Subjects:
Lewis structure
quantum Monte Carlo
wave function analysis
Online Access:Get full text
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Summary:The maxima of squared electronic wave functions |Ψ|2 are analyzed for a number of small molecules. They are in principle observables and show considerable chemical insight from first principles. The maxima contain substantial information about the relative electron positions in a molecule, such as the pairing of opposite spin electrons and the Pauli repulsion which are lost in the electron density. Single bond and double bond as well as polar bond pairs and lone pairs are obtained from the maximum analysis. In many cases, we find a correspondence to the electron arrangements in molecules as assumed by Lewis in 1916. © 2014 Wiley Periodicals, Inc. The maximum of the squared wave function of trans‐butadiene shows distinct electron pairs along the CH and the central CC bond and two characteristic “banana” double bonds for the other two CC bonds.
ISSN:0192-8651
1096-987X
DOI:10.1002/jcc.23561