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N-O and P-O Bond Nature in Hypervalent Compounds: is Bader Analysis Basis-Set and Geometry Independent?

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Quantum Systems in Chemistry and Physics Volume 2

Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 2/3))

Abstract

The Atoms in Molecules Theory description for the X-O (X=N,P) bonds in hypervalent molecules has been tested at various levels and basis sets. Calculations in H3PO, F3PO, H3NO, F3NO molecules have been carried out at the HF, B3LYP and MP2(full) levels using the 3–21G, 3–21G*, 6–31G, 6–31G*, 6–311G, 6–311+G* and 6–311+G(3d,2p) basis sets, showing that polarization functions are essential for an adequate geometrical description of hypervalent molecules, especially when second row atoms are present. The dependence of the numerical parameters at the different bond critical points and the Bader charges on X and O atoms have been studied by the aforementioned methods. The AIM analysis is independent from the chosen level or basissets, when polarization functions are present. The geometry dependence of the X-O Bader analysis has also been tested by performing calculations for H3PO by varying P-O bond lengths. This analysis has been proven as invariable for medium bond lengths variations. The results are also compared with the H3P⋯O van der Waals complex.

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References

  1. Wallmeier, H.; Kutzelnigg, W. J. Amer. Chem. Soc. 1979, 101, 2804.

    CAS  Google Scholar 

  2. Kutzelnigg, W. Angew. Chem. Int. Ed. Engl. 1984, 23, 272.

    Article  Google Scholar 

  3. Kutzelnigg, W. Pure Appl. Chem. 1977, 49, 981.

    CAS  Google Scholar 

  4. Bellinger, J.C.; Houriet, R.; Kern, C.W.; Perret, D.; Weber, J.; Yvernault, T. J. Amer. Chem. Soc. 1985, 107, 5352.

    Google Scholar 

  5. Keil, F.; Kutzelnigg, W. J. Amer. Chem. Soc. 1975, 97, 3623.

    CAS  Google Scholar 

  6. Messmer, R.P. J. Amer. Chem. Soc. 1991, 113, 433.

    Article  CAS  Google Scholar 

  7. Schmidt, M.W.; Gordon, M.S. J. Amer. Chem. Soc. 1985, 107, 1922.

    CAS  Google Scholar 

  8. Boatz, J.A.; Gordon, M.S. J. Comput. Chem. 1986, 7, 306.

    Article  CAS  Google Scholar 

  9. Streitwieser, A.; McDowell, R.S.; Glaser, R. J. Comput. Chem. 1987, 8, 788.

    Article  CAS  Google Scholar 

  10. Streitwieser, A.; Rajca, A.; McDowell, R.S.; Glaser, R. J. Amer. Chem. Soc. 1987, 109, 4184.

    Article  CAS  Google Scholar 

  11. Schneider, W.; Thiel, W.; Komornicki, A. J. Phys. Chem. 1988, 92, 5611.

    CAS  Google Scholar 

  12. Gilheany, D.G. The Chemistry of Organophosphorous Compounds Vol. 2; Wiley-Interscience: Chichester, 1992.

    Google Scholar 

  13. Gilheany, D.G. Chem. Rev. 1994, 94, 1339.

    Article  CAS  Google Scholar 

  14. Kutzelnigg, W. J. Mol. Struct. THEOCHEM 1988, 46, 403.

    CAS  Google Scholar 

  15. Ehrhardt, C.; Ahlrichs, R. Theor. Chim. Acta 1985, 68, 231.

    Article  CAS  Google Scholar 

  16. Heinzmann, R.; Ahlrichs, R. Theor. Chim. Acta 1976, 42, 33.

    Article  CAS  Google Scholar 

  17. Cruickshank, D.W.J.; Eisenstein, M. J. Mol. Structure 1985, 130, 143.

    CAS  Google Scholar 

  18. Cruickshank, D.W.J. J. Mol. Structure 1985, 130, 177.

    CAS  Google Scholar 

  19. Cruickshank, D.W.J.; Eisenstein, M. J. Comput. Chem. 1987, 8, 6.

    Article  CAS  Google Scholar 

  20. Reed, A.E.; Weinhold, F. J. Amer. Chem. Soc. 1986, 108, 3586.

    Article  CAS  Google Scholar 

  21. Reed, A.E.; Schleyer, P.V.R. Chem. Phys. Letters 1987, 133, 553.

    CAS  Google Scholar 

  22. Foster, J.P.; Weinhold, F. J. Amer. Chem. Soc. 1980, 102, 7211.

    Article  CAS  Google Scholar 

  23. Reed, A.E.; Weinstock, R.B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.

    CAS  Google Scholar 

  24. Reed, A.E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736.

    CAS  Google Scholar 

  25. Reed, A.E.; Curtiss, L.A.; Weinhold, F. Chem. Rev. 1988, 88, 899.

    Article  CAS  Google Scholar 

  26. Cooper, D.L.; Cunningham, T.P.; Gerratt, J.; Karadakov, P.B.; Raimondi, M. J. Amer. Chem. Soc. 1994, 116, 4414.

    Article  CAS  Google Scholar 

  27. Schmidt, M.W.; Gordon, M.S. Can. J. Chem. 1985, 63, 1609.

    CAS  Google Scholar 

  28. Reed, A.E.; Schleyer, P.V.R. J. Amer. Chem. Soc. 1990, 112, 1434.

    Article  CAS  Google Scholar 

  29. Schmidt, M.W.; Yabushita, S.; Gordon, M.S. J. Phys. Chem. 1984, 88, 382.

    CAS  Google Scholar 

  30. Guest, M.F.; Hillier, I.H.; Saunders, V.R. J. Chem. Soc., Faraday Trans. 2 1972, 867.

    Google Scholar 

  31. Molina, P.; Alajarin, M.; Leonardo, C.L.; Claramunt, R.M.; Foces-Foces, M.D.L.C.; Cano, F.H.; Catalán, J.; de Paz, J.L.G.; Elguero, J. J. Amer. Chem. Soc. 1989, 111, 355.

    Article  CAS  Google Scholar 

  32. Schultz, P.A.; Messmer, R.P. J. Amer. Chem. Soc. 1993, 115, 10925.

    CAS  Google Scholar 

  33. Schultz, P.A.; Messmer, R.P. J. Amer. Chem. Soc. 1993, 115, 10938.

    CAS  Google Scholar 

  34. Murphy, R.B.; Messmer, R.P. J. Chem. Phys. 1993, 98, 7958.

    CAS  Google Scholar 

  35. Grein, F.; Lawlor, L. Theor. Chim. Acta 1983, 63, 161.

    Article  CAS  Google Scholar 

  36. Cunningham, T.P.; Cooper, D.L.; Gerratt, J.; Karadakov, P.B.; Raimondi, M. Int. J. Quantum Chem. 1996, 60, 393.

    Article  CAS  Google Scholar 

  37. Fan, M.F.; Jia, G.C.; Lin, Z.Y. J. Amer. Chem. Soc. 1996, 118, 9915.

    CAS  Google Scholar 

  38. Platts, J.A.; Howard, S.T.; Bracke, B.R.F. J. Amer. Chem. Soc. 1996, 118, 2726.

    Article  CAS  Google Scholar 

  39. Heinemann, C.; Muller, T.; Apeloig, Y.; Schwarz, H. J. Amer. Chem. Soc. 1996, 118, 2023.

    Article  CAS  Google Scholar 

  40. Hernández-Laguna, A.; Sainz-Díaz, C.I.; Smeyers, Y.G.; de Paz, J.L.G.; Gálvez Ruano, E. J. Phys. Chem. 1994, 98, 1109.

    Google Scholar 

  41. Sainz-Díaz, C.I.; Hernández-Laguna, A.; Smeyers, Y.G. J. Mol. Struct. THEOCHEM 1997, 390, 127.

    Google Scholar 

  42. Dobado, J.A.; Molina, J. J. Phys. Chem. 1994, 98, 1819.

    CAS  Google Scholar 

  43. Dobado, J.A.; Portal, D.; Molina, J. J. Phys. Chem. A 1998, 102, 778.

    Article  CAS  Google Scholar 

  44. Navarro, J.A.R.; Romero, M.A.; Salas, J.M.; Quiros, M.; El-Bahraoui, J.; Molina, J. Inorg. Chem. 1996, 35, 7829.

    Article  CAS  Google Scholar 

  45. El-Bahraoui, J.; Molina, J.; Portal, D. J. Phys. Chem. A 1998, 102, 2443.

    Google Scholar 

  46. Cioslowski, J.; Surján, P.R. J. Mol. Struct. THEOCHEM 1992, 255, 9.

    Article  Google Scholar 

  47. Cioslowski, J.; Mixon, S.T. Inorg. Chem. 1993, 32, 3209.

    Article  CAS  Google Scholar 

  48. Dobado, J.A.; Molina, J.; Martínez-García, H.; Sundberg, M.R. J. Amer. Chem. Soc. 1998, 120, 8461.

    Article  CAS  Google Scholar 

  49. Lee, C.; Yang, W.; Parr, R.G. Phys. Rev. B 1988, 37, 785.

    CAS  Google Scholar 

  50. Becke, A.D. J. Chem. Phys. 1993, 98, 5648.

    CAS  Google Scholar 

  51. Møller, C.; Plesset, M.S. Phys. Rev. 1934, 46, 618.

    Google Scholar 

  52. Gaussian 94, revision C.2. 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.; Cioslowski, B.B.; Stefanov, A.; Nanayakkara, M.; Challacombe, 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.J.P.; Head-Gordon, M.; Gonzalez, C.; Pople, J.A.; Gaussian Inc. 1995, Pittsburgh PA.

    Google Scholar 

  53. Biegler-König, F.W.; Bader, R.F.W.; Tang, T.H. J. Comput. Chem. 1982, 3, 317.

    Google Scholar 

  54. Bader, R.F.W. Atoms in Molecules: a Quantum Theory; Clarendon Press: Oxford, 1990.

    Google Scholar 

  55. Bader, R.F.W. Chem. Rev. 1991, 91, 893.

    Article  CAS  Google Scholar 

  56. Popelier, P.L.A. Comput. Phys. Commun. 1996, 93, 212.

    CAS  Google Scholar 

  57. Grimme, S. J. Amer. Chem. Soc. 1996, 118, 1529.

    Article  CAS  Google Scholar 

  58. Kagann, R.H.; Ozier, I.; Gerry, M.C.L. J. Mol. Spectrosc. 1978, 71, 281.

    Article  CAS  Google Scholar 

  59. Kirchoff, W.H.; Lide, D.R. J. Chem. Phys. 1969, 51, 467.

    Google Scholar 

  60. Moritani, T.; Kuchitsu, K.; Morino, Y. Inorg. Chem. 1971, 10, 344.

    Google Scholar 

  61. Plato, V.; Hartford, W.D.; Hedberg, K. J. Chem. Phys. 1970, 53, 3488.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Grupo de Modelización y Diseño Molecular, Instituto de Biotecnología, Universidad de Granada, Campus Fuentenueva, E-18071, Granada, (Spain)

    J. A. Dobado, Henar Martínez-García & José Molina

  2. Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, A.I. Virtasen aukio 1, Helsinki, Finland, FIN-00014

    Markku R. Sundberg

Authors
  1. J. A. Dobado
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  2. Henar Martínez-García
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  3. José Molina
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  4. Markku R. Sundberg
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Corresponding authors

Correspondence to José Molina or Markku R. Sundberg .

Editor information

Editors and Affiliations

  1. Estación Experimental del Zaidín (C.S.I.C.), Granada, Spain

    Alfonso Hernández-Laguna

  2. Laboratoire de Chimie Physique (C.N.R.S.), Paris, France

    Jean Maruani

  3. Universita di Pisa, Pisa, Italy

    Roy McWeeny

  4. Rutherford Appleton Laboratory, Oxfordshire, UK

    Stephen Wilson

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© 2000 Kluwer Academic Publishers

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Dobado, J.A., Martínez-García, H., Molina, J., Sundberg, M.R. (2000). N-O and P-O Bond Nature in Hypervalent Compounds: is Bader Analysis Basis-Set and Geometry Independent?. In: Hernández-Laguna, A., Maruani, J., McWeeny, R., Wilson, S. (eds) Quantum Systems in Chemistry and Physics Volume 2. Progress in Theoretical Chemistry and Physics, vol 2/3. Springer, Dordrecht. https://doi.org/10.1007/0-306-48145-6_18

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  • DOI: https://doi.org/10.1007/0-306-48145-6_18

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-0-7923-5970-8

  • Online ISBN: 978-0-306-48145-1

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