Orbital Interaction and Chemical Bonds. Polarization in Chemical Reactions

Journal of the American Chemical Society

Volumn 99, Issue 23, 1977, Pages 7424-7432

  Fujimoto, Hiroshi ^a   Inagaki, Satoshi ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0010776285     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00465a004     Document Type: Article

References (45)

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3. K. Fukui, “Theory of Orientation and Stereoselection”, Springer-Verlag, West Berlin, 1974;
4. H. Fujimoto and K. Fukui, “Chemical Reactivity and Reaction Paths”, G. Klopman, Ed., Wiley-lnterscience, New York, N.Y., 1974, p 23.
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21. About an alternative way of obtaining the coefficients, see H. Baba, S. Suzuki, and T. Takemura, J. Chem. Phys., 50, 2078 (1969);
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25. On the importance of excited electron configurations in unimolecular reactions, see the works by Bader, Salem, and Pearson (R. F. W. Bader, Can. J. Chem., 40, 1164 (1962);
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27. R. Pearson, J. Am. Chem. Soc., 91, 1252, 4947 (1969)).
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29. A determinantal wave function [formula omitted] Now it is easy to calculate the integral Hp.q weighted by the normalizing factors due to the MO overlaps by means of the transformed bond orders, in a similar way as the computation of the total electronic energy in the SCF MO theory with orthonormal one-electron functions (H. Fujimoto and N. Kosugi, Bull. Chem. Soc. Jpn., 50, 2209 (1977)).
30. A. Dedieu and A. Veillard, J. Am. Chem. Soc., 94, 6730 (1972). The geometry obtained by Dedieu and Veillard may be somewhat arbitrary.
31. Orbital constants were taken after Stewart, et al. See R. F. Stewart, J. Chem. Phys., 52, 431 (1970);
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35. On the effect of dipolar fields on chemical interactions, see S. Yamabe, S. Kato, H. Fujimoto, and K. Fukui, Theor. Chim. Acta, 30, 327 (1973).
36. One may notice that locally excited configurations participate in the accumulation of electron density in the intermolecular region and, hence, in the formation of chemical bonds between reagent and reactant through the interaction with electron-transferred configurations. The significance of such orbital interactions was discussed recently. See S. Inagaki, H. Fujimoto, and K. Fukui, J. Am. Chem. Soc., 97, 6108 (1975).
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