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Relativistic Effects in Molecular Structure of S-and P-Block Elements

  • Chapter
Strength from Weakness: Structural Consequences of Weak Interactions in Molecules, Supermolecules, and Crystals

Part of the book series: NATO Science Series ((NAII,volume 68))

Abstract

Relativistic quantum theory is well known since Dirac formulated it in 1928. However, relativistic quantum chemical methods have only been developed in the last two decades. Fully relativistic program codes for atoms and molecules are now available. Such program codes make it feasible for the first time to perform calculations for the heavier elements in the periodic table. For these elements relativistic effects cannot be neglected anymore. For example, spin-orbit coupling becomes similar or even larger in size compared to typical bond energies in trans-actinide compounds. The stability of compounds containing heavy elements can change dramatically due to relativistic effects thus influencing both structure and reactivity.

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References

  1. Pyykkö, P. and Desclaux, J.P. (1979) Acc. Chem. Res. 12, 276.

    Article  Google Scholar 

  2. See discussion in Kutzelnigg, W. (2000) Theor. Chem. Acc. 103, 182.

    Article  CAS  Google Scholar 

  3. Pyykkö, P. (1988) Chem. Rev. 88, 563.

    Article  Google Scholar 

  4. Schwerdtfeger, P. and Seth, M. (1998) in Schleyer, P.v.R., Schreiner, P.R., Allinger, N.L., Clark, T., Gasteiger, J., Kollman, P., and Schaefer III, H.F. (eds.), Encyclopedia of Computational Chemistry, Vol. 4, Wiley, New York, pp. 2480–2499.

    Google Scholar 

  5. Schwarz, W.H.E., Schwerdtfeger, P., Snijders, JG., and Baerends, E.J. (1990) J. Phys. B 23, 3225. (b) Schwarz, W.H.E., van Weezenbeck, E., Baerends, E.J., and Snijders, J.G. (1989) J. Phys. B 22, 1515.

    Article  Google Scholar 

  6. Boyd, R.G., Larson, A.C., and Waber, J.T. (1963) Phys. Rev. 129, 1629.

    Article  CAS  Google Scholar 

  7. Saue, T., Enevoldsen, T., Helgaker, T., Jensen, H.J.A., Laerdahl, J.K., Ruud, K., Thyssen, J., and Visscher, L. (1998) DIRAC, A Relativistic ab Initio Electronic Structure Program, Release 3.1, Odense University, Denmark. See also: http://dirac.chem.sdu.dk.

    Google Scholar 

  8. Aerts, P.J., Visser, O., Visscher, L., Merenga, H., de Jong, W.A., and Nieuwpoort, W.C. (1996) Program MOLFDIR, University of Groningen, The Netherlands.

    Google Scholar 

  9. Grant, I.P. and Quiney, H.M. (2000) Int. J. Quantum Chem. 80, 283.

    Article  CAS  Google Scholar 

  10. Pernpointner, M., Visscher, L., de Jong, W.A., and Broer, R. (2000) J. Comput. Chem. 21, 1176.

    Article  CAS  Google Scholar 

  11. Faegri Jr., K. (2001) Theor. Chem. Acc. 105, 252.

    Article  CAS  Google Scholar 

  12. Hess, B.A. (1986) Phys. Rev. A 33, 3742.

    Article  CAS  Google Scholar 

  13. van Lenthe, E., Snijders, J.G., and Baerends, E.J. (1996) J. Chem. Phys. 105, 6505.

    Article  Google Scholar 

  14. Kutzelnigg, W. and Liu, W. (2000) J. Chem. Phys. 112, 3540.

    Article  CAS  Google Scholar 

  15. Andersson, K., Barysz, M., Bernhardsson, A., Blomberg, M.R.A., Cooper, D.L., Fleig, T., Fülscher, MP., de Graaf, C, Hess, B.A., Karlström, G., Lindh, R., Malmqvist, P.-Å., Neogrády, P., Olsen, J., Roos, B.O., Sadlej, A.J., Schütz, M., Schimmelpfennig, B., Sejo, L., Serran-Andrés, L., Stålling, J., Thorsteinsson, T., Veryazov, V., and Widmark, P.-O. (2000) Program MOLCAS5, Sweden. See also: http://www.teokem.lu.se/molcas.

  16. Program ADF (1999) Scientific Computing & Modelling NV, Vrije Universiteit, Amsterdam, The Netherlands. See also: http://www.scm.com.

    Google Scholar 

  17. Guest, M.F., van Lenthe, J.H., Kendrick, J., Schoffel, K., Sherwood, P., Amos, R.D., Buenker, R.J., van Dam, H., Dupuis, M., Handy, N.C., Hillier, LH., Knowles, P.J., Bonacic-Koutecký, V., von Niessen, W., Harrison, R.J., Rendell, A.P., Saunders, V.R., Stone, A.J., and Tozer, D. (2000) Program GAMESS-UK, Version 6, Warrington, UK. See also: http://www.dl.ac.uk/CCP/CCPl/gamess.html.

  18. Hess, B.A., Marian, CM., and Peyerimhoff, S.D. (1995) in Yarkony, D.R. (ed.), Modern Electronic Structure Theory, Part 1, Advanced Series in Physical Chemistry, Vol. 2, World Scientific, Singapore, pp. 152–278.

    Chapter  Google Scholar 

  19. Fleig, T., Olsen, J., and Marian, CM. (2001) J. Chem. Phys. 114, 4775.

    Article  CAS  Google Scholar 

  20. Frenking, G., Antes, L, Böhme, M., Dapprich, S., Ehlers, A.W., Jonas, V., Neuhaus, A., Veldkamp, A., and Vyboishchikov, S.F. (1996) in Lipkowitz, K.B. and Boyd, D.B. (eds.), Reviews in Computational Chemistry, Vol. 8, VCH, Weinheim, pp. 63–144.

    Chapter  Google Scholar 

  21. Visscher, L., Dyall, K.G., and Lee, T.J. (1995) Int. J. Quantum Chem., Quantum Chem.Symp. 29, 411.

    Article  CAS  Google Scholar 

  22. Schwerdtfeger, P., Brown, J.R., Laerdahl, J.K., and Stol;, H. (2000) J. Chem. Phys. 113, 7110.

    Article  CAS  Google Scholar 

  23. Ziegler, T., Tschinke, V, Baerends, E.J., Snijders, J.G., and Ravenek, W. (1989) J. Phys. Chem. 93, 3050.

    Article  CAS  Google Scholar 

  24. Strömberg, D. and Wahlgren, U. (1990) Chem. Phys. Lett. 169, 109.

    Article  Google Scholar 

  25. Schwerdtfeger, P. (1991) Chem. Phys. Lett. 183, 457.

    Article  CAS  Google Scholar 

  26. Häberlen, O.D. and Rösch, N. (1992) Chem. Phys. Lett. 199, 491.

    Article  Google Scholar 

  27. Bastug, T., Heinemann, D., Sepp, W.-D., Kolb, D., and Fricke, B. (1993) Chem. Phys. Lett. 211, 119.

    Article  CAS  Google Scholar 

  28. Hess, B.A. (1997) Ber. Bunsenges. Phys. Chem. 101, 1.

    Article  CAS  Google Scholar 

  29. van Lenthe, E., Baerends, E.J., and Snijders, J.G. (1994) J. Chem. Phys. 101, 9783.

    Article  Google Scholar 

  30. Park, C and Almlöf, J.E. (1994) Chem. Phys. Lett. 231, 269.

    Article  CAS  Google Scholar 

  31. van Wüllen, C. (1995) J. Chem. Phys. 103, 3589.

    Article  Google Scholar 

  32. Wesendrup, R., Laerdahl, J.K., and Schwerdtfeger, P. (1999) J. Chem. Phys. 110 , 9457.

    Article  CAS  Google Scholar 

  33. Desclaux, J.P. and Pyykkö, P. (1976) Chem. Phys. Lett. 39, 300.

    Article  CAS  Google Scholar 

  34. If available the bond distances were taken from Huber, K.P. and Herzberg, G. (1979) Molecular Spectra and Molecular Structure Constants of Diatomic Molecules, Van Nostrand, New York. Otherwise the distances were obtained from scalar relativistic pseudopotential calculations in our group or from the following published computed values: (a) Russon, L.M., Rothschopf, G.K., Morse, M.D., Boldyrev, A.I., and Simons, J. (1998) J. Chem. Phys. 109, 6655. (b) Gleichmann, M.M. and Hess, B.A. (1994) J. Chem. Phys. 101, 9691. (c) Mouche, A.R. and Aubert-Frécon, M. (1994) J. Chem. Phys. 100, 938. (d) Bauschlicher Jr., C.W., Langhoff, S.R., and Partridge, H. (1992) J. Chem. Phys. 96, 1240. (e) Boldyrev, Ai. and Simons, J. (1997) Mol Phys. 92, 365. (f) Kaupp, M. and von Schnering, H.G. (1994) Inorg. Chem. 33, 4179. (g) van Hemert, M.C., Azinovic, D., Li, X., Milosevic, S., and Pichler, G. (1992) Chem. Phys. Lett. 200, 97. (h) Urban, M. and Sadlej, A.J. (1995) J. Chem. Phys. 103, 9692. (i) Liu, W., Van Wüllen, C, Han, Y.-K., Choi, Y.J., and Lee, Y.S. (2001) Adv. Quantum Chem., in press, (j) Nash, CS. and Bursten, B.E. (1999) J. Phys. Chem. A 103, 632. (k) Han, Y.-K., Bae, C, and Lee, Y.S. (1999) J. Chem. Phys. 110, 8969. (1) Nash, C.S. and Bursten, B.E. (1999) J. Phys. Chem. 103, 402.

    Google Scholar 

  35. Schwarz, W.H.E. (1987) Phys. Scr. 36, 403.

    Article  CAS  Google Scholar 

  36. Seth, M., Dolg, M., Fulde, P., and Schwerdtfeger, P. (1995) J. Am. Chem. Soc. 117, 6597.

    Article  CAS  Google Scholar 

  37. Liao, M.-S., Zhang, Q.-E., and Schwarz, W.H.E. (1995) Inorg. Chem. 34, 5597.

    Article  CAS  Google Scholar 

  38. Schädel, M., Brüchle, W., Dressler, R., Eichler, B., Gäggeler, H.W., Günther, R., Gregorich, K.E., Hoffman, D.C., Hübener, S., Jost, D.T., Kratz, J.V., Paulus, W., Schumann, D., Timokhin, S„ Trautmann, N., Türler, A., Wirth, G., and Yakuschev, A. (1997) Nature 388, 55.

    Article  Google Scholar 

  39. Seth, M. and Schwerdtfeger, P. (2000) Chem. Phys. Lett. 318, 314.

    Article  CAS  Google Scholar 

  40. Lupinetti, A.J., Jonas, V., Thiel, W., Strauss, S.H., and Frenking, G. (1999) Chem. Eur. J. 5, 2573; and references therein.

    Article  CAS  Google Scholar 

  41. Kaupp, M. and von Schnering, H.G. (1993) Angew. Chem., Int. Ed. Engl. 32, 861. (b) Kaupp, M., Dolg, M., Stoll, H., and von Schnering, H.G. (1994) Inorg. Chem. 33, 2122.

    Article  Google Scholar 

  42. Schwerdtfeger, P., Boyd, P.D.W., Brienne, S., and Burrell, A.K. (1992) Inorg. Chem. 31, 3411.

    Article  CAS  Google Scholar 

  43. van Eijndhoven, J.C.M.T. and Verschoor, G.C. (1974) Mater. Res. Bull. 9, 1667.

    Article  Google Scholar 

  44. Seth, M., Faegri, K., and Schwerdtfeger, P. (1999) J. Chem. Phys. 111, 6422.

    Article  CAS  Google Scholar 

  45. Schwerdtfeger, P., Heath, G.A., Dolg, M., and Bennett, M.A. (1992) J. Am. Chem. Soc. 114, 7518.

    Article  CAS  Google Scholar 

  46. Schwarz, W.H.E. (1990) in Maksic, Z. (ed.), Theoretical Models of Chemical Bonding, Springer, Berlin, pp. 593–643.

    Google Scholar 

  47. Schwerdtfeger, P. and Hunt, P. (1999) in Hargittai, M. and Hargittai, I. (eds.), Advances in Molecular Structure Research, Vol. 5, JAI Press, Stamford, pp. 223–262.

    Chapter  Google Scholar 

  48. Foley, J.B., Bruce, A.E., and Bruce, M.R.M. (1995) J. Am. Chem. Soc. 117, 9596.

    Article  CAS  Google Scholar 

  49. Schwerdtfeger, P., Bruce, A.E., and Bruce, M.R.M. (1998) J. Am. Chem. Soc. 120 , 6587.

    Article  CAS  Google Scholar 

  50. Pyykkö, P. (1997) Chem. Rev. 97, 597. (b) Pyykkö, P., Li, I, and Runeberg, N. (1994) Chem. Phys. Lett. 218, 133. (c) Pyykkö, P. and Zhao, Y. (1991) Angew. Chem., Int. Ed. Engl. 30, 604. (d) Li, J. and Pyykkö, P. (1992) Chem. Phys. Lett. 197, 586. (e) Pyykkö, P., Schneider, W., Bauer, A., Bayler, A., and Schmidbaur, H. (1997) Chem. Commun. 1111. (f) Pyykkö, P., Runeberg, N., and Mendizabal, F. (1997) Chem. Eur. J. 3, 1451. (g) Pyykkö, P. and Mendizabal, F. (1997) Chem. Eur. J. 3, 1458.

    Article  Google Scholar 

  51. Schwerdtfeger, P. (1989) J. Am. Chem. Soc. 111, 7261.

    Article  CAS  Google Scholar 

  52. Söhnel, T., Brown, R., Kloo, L., and Schwerdtfeger, P. (2001) Chem. Eur. J. 7, 3167.

    Article  Google Scholar 

  53. Wesendrup, R. and Schwerdtfeger, P. (2001) Inorg. Chem. 40, 3351.

    Article  CAS  Google Scholar 

  54. Seppelt, K., personal communication.

    Google Scholar 

  55. Seth, M., Schwerdtfeger, P., and Dolg, M. (1997) J. Chem. Phys. 106, 3623.

    Article  CAS  Google Scholar 

  56. Drago, R.S. (1958) J. Phys. Chem. 62, 353.

    Article  CAS  Google Scholar 

  57. Seth, M., Faegri, K., and Schwerdtfeger, P. (1998) Angew. Chem., Int. Ed. Engl. 37, 2493.

    Article  CAS  Google Scholar 

  58. Vickery, J.C., Olmstead, M.M., Fung, E.Y., and Balch, A.L. (1997) Angew. Chem., Int Ed. Engl. 36, 1179. (b) Fernández, E.J., Gimeno, M.C., Laguna, A., López-de-Luzuriaga, IM., Monge, M., Pyykkö, P., and Sundholm, D. (2000) J. Am. Chem. Soc. 122, 7287.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand

    Peter Schwerdtfeger

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  1. Peter Schwerdtfeger
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Editors and Affiliations

  1. University of L’Aquila, Italy

    Aldo Domenicano

  2. Budapest University of Technology and Economics, Hungary

    István Hargittai

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Schwerdtfeger, P. (2002). Relativistic Effects in Molecular Structure of S-and P-Block Elements. In: Domenicano, A., Hargittai, I. (eds) Strength from Weakness: Structural Consequences of Weak Interactions in Molecules, Supermolecules, and Crystals. NATO Science Series, vol 68. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0546-3_9

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  • DOI: https://doi.org/10.1007/978-94-010-0546-3_9

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