Abstract
The population analysis based on occupation numbers, originally proposed by Davidson, is briefly reviewed. A new way is proposed to determine modified AOs and to characterize hypervalent contributions. This is discussed in application to the molecules NSF, NSF3, SF6, OPCl, OPCl2, O2PCl, SO2, ClO −4 . It is the main objective of this work to investigate the connection between shared electron numbers σ — considered as a measure of covalent bond strength — and bond energies, σ is found to be a reliable measure of bond energies.
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References
Mulliken, R. S.: J. Chem. Phys. 23, 1833 (1955)
Davidson, E. R.: J. Chem. Phys. 46, 3320 (1967)
Heinzmann, R., Ahlrichs, R.; Theoret. Chim. Acta (Berl.) 42, 33 (1976)
Roby, K. R.: Molec. Phys. 27, 81 (1974)
Cruickshank, D. W. J., Avramides, E. J.: Phil. Trans. R. Soc. Lond. A304, 533 (1982)
Schnöckel, H., Schunck, S.: private communication
Kutzelnigg, W.: Einführung in die Theoretische Chemie II. Verlag Chemie, Weinheim 1978
Pauling, L.: Nature of the Chemical Bond. Cornell University Press 1960
Kutzelnigg, W., Staemmler, V., Gelus, M.: Chem. Phys. Letters 13, 496 (1972)
Benson, S. W.: J. Chem. Educ. 42, 502 (1965)
Herzberg, G.: Molecular Spectra and Molecular Structure I. D. van Nostrand 1955
Hanna, M.: Quantum Mechanics in Chemistry. Benjamin 1969
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Ehrhardt, C., Ahlrichs, R. Population analysis based on occupation numbers II. Relationship between shared electron numbers and bond energies and characterization of hypervalent contributions. Theoret. Chim. Acta 68, 231–245 (1985). https://doi.org/10.1007/BF00526774
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DOI: https://doi.org/10.1007/BF00526774