Structural Chemistry

, Volume 9, Issue 4, pp 243–247 | Cite as

Bond Length–Electron Density Relationships: From Covalent Bonds to Hydrogen Bond Interactions

  • Ibon AlkortaEmail author
  • Isabel Rozas
  • José Elguero


It is possible to treat bond distances of covalent C-H bonds and C⋯H hydrogen bonds simultaneously assuming a logarithmic relationship with the electron density at the bond critical point. Similar relationships have been found for other X-H/X⋯H bonds. The data used for obtaining these equations have been determined theoretically. All the systems have been fully optimized and their electron densities calculated at the B3LYP/6-311 + + G(d,p) level.

Hydrogen bonds electron density bond critical points DFT calculations Pauling's bond order bond length 


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  1. 1. (a)
    Pauling, L. J. Am. Chem. Soc. 1927, 49, 765–790; (b) Pauling, L. J. Am. Chem. Soc. 1929, 51, 1010–1026; (c) Pauling, L.; Brockway, L. O.; Beach, J. Y. J. Am. Chem. Soc. 1935, 57, 2705–2709; (d) Pauling, L. The Nature of the Chemical Bond; Cornell University Press: Ithaca, NY, 1945; (e) Pauling, L. General Chemistry, 3rd ed.; W. H. Freeman: San Francisco, 1970.Google Scholar
  2. 2. (a)
    Dunitz, J. D. X-Ray Analysis and the Structure of Organic Molecules, p. 344; Cornell University Press: Ithaca, NY, 1979; (b) Structure Correlation, Bürgi, H.-B.; Dunitz, J. D., eds.; Vol. 1, pp. 195, 225, 305; VCH Publishers: Weinheim, 1994.Google Scholar
  3. 3. (a)
    Brown, I. D. Acta Crystallogr. Sect. B 1992, 48, 553–572; (b) Grabowski, S. J. Croat. Chim. Acta 1988, 61, 815–819.Google Scholar
  4. 4.
    Gaussian 94, Revision B.3; Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A.; Gaussian, Inc.: Pittsburgh, PA, 1995.Google Scholar
  5. 5.
    Krishman, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1984, 80, 650–654.Google Scholar
  6. 6.
    Becke, A. D. J. Chem. Phys. 1993, 98, 5648–5652.CrossRefGoogle Scholar
  7. 7.
    Bader, R. F. W. Atoms in Molecules. A Quantum Theory; Oxford University Press: New York, 1990.Google Scholar
  8. 8.
    Bieger-Konig, F. W.; Bader, R. F. W.; Tang, T. H. J. Comput. Chem. 1982, 3, 317–328.Google Scholar
  9. 9.
    Paolini, J. P. J. Comput. Chem. 1990, 11, 1160–1163.Google Scholar
  10. 10.
    Bader, R. F. W.; Tang, T. H.; Tal, Y.; Bieger-Konig, F. W. J. Am. Chem. Soc. 1982, 104, 946–952.Google Scholar
  11. 11.
    Knop, O.; Boyd, R. J.; Choi, S. C. J. Am. Chem. Soc. 1988, 110, 7299–7301.Google Scholar
  12. 12.
    Boyd, R. J.; Choi, S. C. Chem. Phys. Lett. 1985, 120, 80–85.Google Scholar
  13. 13.
    Boyd, R. J.; Choi, S. C. Chem. Phys. Lett. 1986, 129, 62–65.Google Scholar
  14. 14.
    Ramos, M.; Alkorta, I.; Elguero, J.; Golubev, N. S.; Denisov, G. S.; Benedict, H.; Limbach, H. H. J. Chem. Phys. A, 1997, 101, 9791–9800.Google Scholar
  15. 15.
    Roversi, P.; Barzaghi, M.; Merati, F.; Destro, R. Can. J. Chem. 1996, 74, 1145–1161.Google Scholar

Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  1. 1.Instituto de Quimica MédicaCSICMadridSpain

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