Curly arrows, electron flow, and reaction mechanisms from the perspective of the bonding evolution theory
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comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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Title
Curly arrows, electron flow, and reaction mechanisms from the perspective of the bonding evolution theoryAuthor (s)
Date
2017Publisher
Royal Society of ChemistryISSN
1463-9076; 1463-9084Bibliographic citation
Phys. Chem. Chem. Phys., 2017, 19, 29031Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/acceptedVersionAbstract
Despite the usefulness of curly arrows in chemistry, their relationship with real electron density flows
is still imprecise, and even their direct connection to quantum chemistry is still controversial. The
paradi ... [+]
Despite the usefulness of curly arrows in chemistry, their relationship with real electron density flows
is still imprecise, and even their direct connection to quantum chemistry is still controversial. The
paradigmatic description – from first principles – of the mechanistic aspects of a given chemical process
is based mainly on the relative energies and geometrical changes at the stationary points of the potential
energy surface along the reaction pathway; however, it is not sufficient to describe chemical systems
in terms of bonding aspects. Probing the electron density distribution during a chemical reaction can
provide important insights, enabling us to understand and control chemical reactions. This aim has
required an extension of the relationships between the concepts of traditional chemistry and those of
quantum mechanics. Bonding evolution theory (BET), which combines the topological analysis of the
electron localization function (ELF) and Thom’s catastrophe theory (CT), provides a powerful method
that offers insight into the molecular mechanism of chemical rearrangements. In agreement with the
laws of physical and aspects of quantum theory, BET can be considered an appropriate tool to tackle
chemical reactivity with a wide range of possible applications. In this work, BET is applied to address a
long-standing problem: the ability to monitor the flow of electron density. BET analysis shows a
connection between quantum mechanics and bond making/forming processes. Likewise, the present
approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds
and provides detailed physical grounds for this type of representation. We demonstrate this procedure
using the test set of prototypical examples of thermal ring apertures, and the degenerated Cope
rearrangement of semibullvalene. [-]
Is part of
Phys. Chem. Chem. Phys., 2017, 19Investigation project
PrometeoII/ 2014/022 ; ACOMP/2015/1202 ; UJI-B2016-25 ; CTQ2015-65207-PRights
http://rightsstatements.org/vocab/CNE/1.0/
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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- QFA_Articles [825]