Literature DB >> 24880263

Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion.

Michael W Schmidt1, Joseph Ivanic2, Klaus Ruedenberg1.   

Abstract

An analysis based on the variation principle shows that in the molecules H2 (+), H2, B2, C2, N2, O2, F2, covalent bonding is driven by the attenuation of the kinetic energy that results from the delocalization of the electronic wave function. For molecular geometries around the equilibrium distance, two features of the wave function contribute to this delocalization: (i) Superposition of atomic orbitals extends the electronic wave function from one atom to two or more atoms; (ii) intra-atomic contraction of the atomic orbitals further increases the inter-atomic delocalization. The inter-atomic kinetic energy lowering that (perhaps counter-intuitively) is a consequence of the intra-atomic contractions drives these contractions (which per se would increase the energy). Since the contractions necessarily encompass both, the intra-atomic kinetic and potential energy changes (which add to a positive total), the fact that the intra-atomic potential energy change renders the total potential binding energy negative does not alter the fact that it is the kinetic delocalization energy that drives the bond formation.

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Year:  2014        PMID: 24880263      PMCID: PMC4032414          DOI: 10.1063/1.4875735

Source DB:  PubMed          Journal:  J Chem Phys        ISSN: 0021-9606            Impact factor:   3.488


  8 in total

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Authors:  T Bitter; K Ruedenberg; W H E Schwarz
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Journal:  J Chem Phys       Date:  2009-05-28       Impact factor: 3.488

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Journal:  J Phys Chem A       Date:  2009-03-12       Impact factor: 2.781

5.  A comprehensive analysis of molecule-intrinsic quasi-atomic, bonding, and correlating orbitals. I. Hartree-Fock wave functions.

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Journal:  J Chem Phys       Date:  2013-12-21       Impact factor: 3.488

6.  Worlds apart in chemistry: a personal tribute to J. C. Slater.

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Journal:  J Phys Chem A       Date:  2011-07-18       Impact factor: 2.781

7.  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

8.  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 in total
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