Literature DB >> 35680893

The role of references and the elusive nature of the chemical bond.

Ángel Martín Pendás1, Evelio Francisco2.   

Abstract

Chemical bonding theory is of utmost importance to chemistry, and a standard paradigm in which quantum mechanical interference drives the kinetic energy lowering of two approaching fragments has emerged. Here we report that both internal and external reference biases remain in this model, leaving plenty of unexplored territory. We show how the former biases affect the notion of wavefunction interference, which is purportedly recognized as the most basic bonding mechanism. The latter influence how bonding models are chosen. We demonstrate that the use of real space analyses are as reference-less as possible, advocating for their use. Delocalisation emerges as the reference-less equivalent to interference and the ultimate root of bonding. Atoms (or fragments) in molecules should be understood as a statistical mixture of components differing in electron number, spin, etc.
© 2022. The Author(s).

Entities:  

Year:  2022        PMID: 35680893      PMCID: PMC9184482          DOI: 10.1038/s41467-022-31036-6

Source DB:  PubMed          Journal:  Nat Commun        ISSN: 2041-1723            Impact factor:   17.694


  31 in total

1.  Quadruple bonding in C2 and analogous eight-valence electron species.

Authors:  Sason Shaik; David Danovich; Wei Wu; Peifeng Su; Henry S Rzepa; Philippe C Hiberty
Journal:  Nat Chem       Date:  2012-01-29       Impact factor: 24.427

2.  Description of Polar Chemical Bonds from the Quantum Mechanical Interference Perspective.

Authors:  Felipe Fantuzzi; Marco Antonio Chaer Nascimento
Journal:  J Chem Theory Comput       Date:  2014-06-10       Impact factor: 6.006

3.  Interacting Quantum Atoms:  A Correlated Energy Decomposition Scheme Based on the Quantum Theory of Atoms in Molecules.

Authors:  M A Blanco; A Martín Pendás; E Francisco
Journal:  J Chem Theory Comput       Date:  2005-11       Impact factor: 6.006

Review 4.  Chemical Bonding from the Statistics of the Electron Distribution.

Authors:  Ángel Martín Pendás; Evelio Francisco
Journal:  Chemphyschem       Date:  2019-08-30       Impact factor: 3.102

5.  One molecule, two atoms, three views, four bonds?

Authors:  Sason Shaik; Henry S Rzepa; Roald Hoffmann
Journal:  Angew Chem Int Ed Engl       Date:  2013-01-30       Impact factor: 15.336

6.  Why does electron sharing lead to covalent bonding? A variational analysis.

Authors:  Klaus Ruedenberg; Michael W Schmidt
Journal:  J Comput Chem       Date:  2007-01-15       Impact factor: 3.376

7.  Covalent bonding: the fundamental role of the kinetic energy.

Authors:  George B Bacskay; Sture Nordholm
Journal:  J Phys Chem A       Date:  2013-08-02       Impact factor: 2.781

8.  Questioning the orbital picture of magnetic spin coupling: a real space alternative.

Authors:  A Martín Pendás; E Francisco
Journal:  Phys Chem Chem Phys       Date:  2022-01-04       Impact factor: 3.676

9.  Energy decomposition analysis of single bonds within Kohn-Sham density functional theory.

Authors:  Daniel S Levine; Martin Head-Gordon
Journal:  Proc Natl Acad Sci U S A       Date:  2017-11-20       Impact factor: 11.205

10.  Spin resolved electron number distribution functions: how spins couple in real space.

Authors:  A Martín Pendás; E Francisco; M A Blanco
Journal:  J Chem Phys       Date:  2007-10-14       Impact factor: 3.488

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