Abstract
It is shown that the chemist's concept of valency can be put in quantum mechanical language. Such a quantification of valency opens up possibilities of new applications which are briefly reviewed. Valency is related to the equilibrium geometry of the molecule through a maximum valency principle. This principle, combined with the idea of molecular orbital valencies, provides a theoretical foundation for the well known Walsh diagrams. Valency can be used as an index of chemical reactivity and valency changes in a reaction can be used to determine the radical nature of intermediates and transition states as well as to indicate the allowed or forbidden nature of reaction paths. Molecular strain may be related to the loss of sigma valency.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Armstrong D R, Perkins P G and Stewart J J 1973J. Chem. Soc. Dalton Trans. 838, 2273
Baud N L and Cessac J, 1977J. Am. Chem. Soc. 99 942
Buenker R J and Peyerimhoff S D 1974Chem. Rev. 74 127
Coulson C A and Deb B M 1971Int. J. Quantum Chem. 5 411
Coulson C A and Moffitt W E 1949Philos. Mag. (London) 40 1
Döhnert D and Koutecky J 1980J Am. Chem. Soc. 102 1789
Gopinathan M S and Jug K 1983Theor. Chim Acta 63, 497, 511
Gopinathan M S, Siddarth P and Ravimohan C 1986Theor. Chim. Acta (communicated)
Jug K 1984J. Comput. Chem. 5 555
Jug K and Gopinathan M S 1985Theor Chim. Acta 68 343
Mayer I 1985Theor. Chim. Acta 67 315
Mulliken R S 1942Rev. Mod. Phys. 14 204
Natiello M A, Realead H F and Medrans J A 1985J. Comput. Chem. 6 108
Ravimohan C 1984Quantum chemical studies on the bonding nature and valency of molecular orbitals, Ph.D. Thesis, Indian Institute of Technology, Madras
Salem L and Rowland C 1972Angew. Chem. 84 86
Semenov S G 1980 inTheory of valency in progress (ed.) V. Kuznetsov (Moscow: Mir Publishers) p. 150
Siddarth P 1984 M. Sc. Dissertation, Indian Institute of Technology, Madras
Stenkamp L Z and Davidson E R 1973Theor. Chim. Acta 30 283
Walsh A D 1953.J. Chem. Soc. 2260
Wiberg K B, Ellison G B and Wendelski J J 1976J. Am. Chem. Soc. 98 1212
Author information
Authors and Affiliations
Additional information
Dedicated to Professor Sadhan Basu on the occasion of his 65th birth anniversary.
Rights and permissions
About this article
Cite this article
Gopinathan, M.S. The quantum chemistry of valency. Proc. Indian Acad. Sci. (Chem. Sci.) 96, 167–176 (1986). https://doi.org/10.1007/BF02974149
Issue Date:
DOI: https://doi.org/10.1007/BF02974149