Abstract
Reviewed in historical context, bond order emerges as a vaguely defined concept without a clear theoretical basis. As an alternative, the spherical standing-wave model of the extranuclear electronic distribution on an atom provides a simple explanation of covalent bond order as arising from the constructive and destructive interference of wave patterns. A quantitative measure derives from a number pattern that relates integer and half-integer bond orders through series of Fibonacci numbers, consistent with golden-spiral optimization. Unlike any previous definition of bond order, this approach is shown to predict covalent bond length, dissociation energy and stretching force constants for homonuclear interactions that are quantitatively correct. The analysis is supported by elementary number theory and involves atomic number and the golden ratio as the only parameters. Validity of the algorithm is demonstrated for heteronuclear interactions of any order. An exhaustive comparison of calculated dissociation energies and interatomic distance in homonuclear diatomic interaction, with experimental data from critical review, is tabulated. A more limited survey of heteronuclear interactions confirms that the numerical algorithms are generally valid. The large group of heteronuclear hydrides is of particular importance to demonstrate the utility of the method, and molecular hydrogen is treated as a special case. A simple formula that describes the mutual polarization of heteronuclear pairs of atoms, in terms of valence densities derived from a spherical-wave structure of extranuclear electronic charge, is used to calculate the dipole moments of diatomic molecules. Valence density depends on the volume of the valence sphere as determined by the atomic ionization radius, and the interatomic distance is determined by the bond order of the diatomic interaction. The results are in satisfactory agreement with literature data and should provide a basis for the calculation of more complex molecular dipole moments. The diatomic CO is treated as a special case, characteristic of all interactions traditionally identified as dative bonds.
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Notes
- 1.
A bond is stretched by external forces, such as steric interactions, only until it flips spontaneously into the wave pattern that stabilizes lower bond order.
References
Boeyens JCA (1973) J S Afr Chem Inst 26:94
Meyer AM (1988) J Mol Struct (Theochem) 179:83
Boeyens JCA (1980) S Afr J Chem 33:14
Boeyens JCA (2005) New theories for chemistry. Elsevier, Amsterdam
Boeyens JCA (2008) Chemistry from first principles. Springer, Dordrecht, Heidelberg, London, New York
Boeyens JCA (2013) Atomic structure, Struct Bond 148:71
Lide DR (ed) Handbook of chemistry and physics, 86th edn. CRC Press, Boca Raton.
Kekulé A (1861) Lehrbuch der Organiaschen Chemie. Enke, Erlangen.
Meyer V (1888) Chem Ber 21:964, 1620
Stewart AW (1922) Some physico-chemical themes. Longmans, London
Sommerfeld A (1924) Atombau und Spektrallinien, 4th edn. Vieweg, Braunschweig
Pauling L (1960) Nature of the chemical bond, 3rd edn. Cornell University Press, Ithaca, p 113
Boeyens JCA, Schutte CJH (2012) In: Putz MV (ed) Chemical information and computational challenges in 21st century. Nova, New York
Putz MV (ed) (2012) Chemical information and computational challenges in 21st century. Nova, New York
Boeyens JCA (1982) J Crystallogr Spectr Res 12:245
Boeyens JCA, Ledwidge DJ (1983) Inorg Chem 22:3587
Boeyens JCA (1978) S Afr J Chem 31:121
Boeyens JCA (1994) J Chem Soc Faraday Trans 90:3377
Boeyens JCA (2008) Z Naturforsch 63b:199
Boeyens JCA, Levendis DC (2008) Number theory and the periodicity of matter. Springer.com
Boeyens JCA, O’Neill FMM (1995) Inorg Chem 34:1988
Boeyens JCA, O’Neill FMM (1998) Inorg Chem 37:5352
Bacsa J, Boeyens JCA (2000) J Organomet Chem 596:159
Boeyens JCA (1985) Inorg Chem 24:4149
Boeyens JCA, Cotton FA, Han S (1985) Inorg Chem 24:1750
Boeyens JCA (2010) Int J Mol Sci 11:4267
Boeyens JCA (2009) Phys Essays, 22:493
Boeyens JCA (2010) Chemical cosmology. Springer, Dordrecht, Heidelberg, London, New York
Cotton FA, Walton RA (1982) Multiple bonds between metal atoms. Wiley, New York
Schaeffer HF III (1972) The electronic structure of atoms and molecules. Addison-Wesley, Reading
Popper KR (1992) Quantum theory and the schism in physics. Routledge, London
Acknowledgements
I gratefully acknowledge the influence of Peter Comba, the only internationally renowned scientist who not only indulged but actively encouraged my maverick views for almost two decades.
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Boeyens, J.C.A. (2013). Covalent Interaction. In: Boeyens, J., Comba, P. (eds) Electronic Structure and Number Theory. Structure and Bonding, vol 148. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-31977-8_5
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DOI: https://doi.org/10.1007/978-3-642-31977-8_5
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