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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28 May 2014
Research Article|
May 23 2014
Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion
Michael W. Schmidt;
Michael W. Schmidt
1Department of Chemistry and Ames Laboratory USDOE,
Iowa State University
, Ames, Iowa 50011, USA
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Joseph Ivanic;
Joseph Ivanic
2
Advanced Biomedical Computing Center
, Information Systems Program, Leidos Biomedical Research, Inc., Frederick National Laboratory for Cancer Research, Frederick, Maryland 21702, USA
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Klaus Ruedenberg
Klaus Ruedenberg
a)
1Department of Chemistry and Ames Laboratory USDOE,
Iowa State University
, Ames, Iowa 50011, USA
Search for other works by this author on:
Michael W. Schmidt
1
Joseph Ivanic
2
Klaus Ruedenberg
1,a)
1Department of Chemistry and Ames Laboratory USDOE,
Iowa State University
, Ames, Iowa 50011, USA
2
Advanced Biomedical Computing Center
, Information Systems Program, Leidos Biomedical Research, Inc., Frederick National Laboratory for Cancer Research, Frederick, Maryland 21702, USA
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 140, 204104 (2014)
Article history
Received:
February 15 2014
Accepted:
April 29 2014
Citation
Michael W. Schmidt, Joseph Ivanic, Klaus Ruedenberg; Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion. J. Chem. Phys. 28 May 2014; 140 (20): 204104. https://doi.org/10.1063/1.4875735
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