Advertisement

Curve Crossing Diagrams as General Models for Chemical Reactivity and Structure

  • Sason S. Shaik
  • Philippe C. Hiberty
Chapter
  • 128 Downloads
Part of the Perspectives in Antisense Science book series (BSPS, volume 139)

Abstract

Reactivity and structure are two important branches of chemistry which are conceptualized in terms of potential energy profiles on hypersurfaces. Potential energy profiles and surfaces are wonderful concepts but they replace the chemical complexity by a mathematical complexity. We are left, in fact, with the goal of understanding potential energy profiles and surfaces as the means to conceptualize chemistry. This has been an important conceptual goal in quantum chemistry [1] eversince the pioneering studies in the first half of this century [2].

Keywords

Valence Bond Reaction Coordinate Charge Transfer State Potential Energy Profile Lewis Structure 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Salem L (1982) Electrons in chemical reactions, Wiley, New York, Chaps. 2, 4–6, and 8Google Scholar
  2. 2.(a)
    Wigner E, Witmer EE (1928) Z Physik 51: 851 (b) Evans MG, Polanyi M (1938) Trans Far Soc 34: 11 (c) Eyring H (1935) J Chem Phys 3: 107 (d) Laidler KJ, Shuler KE (1951) Chem Rev 48: 153CrossRefGoogle Scholar
  3. 3.
    Shaik SS (1981) J Am Chem Soc 103: 3692CrossRefGoogle Scholar
  4. 4.(a)
    Pross A, Shaik SS (1983) Ace Chem Res 16: 363 (b) Shaik SS (1985) Prog Phys Org Chem 15: 197 (c) Pross A (1985) Adv Phys Org Chem 21: 99CrossRefGoogle Scholar
  5. 5.(a)
    Shaik SS (1990) Acta Chem Scand 44: 205 (b) Shaik SS, Schlegel HB, Wolfe S (1991) Theoretical aspecs of physical organic chemistry: Application to the SN2 transition state, Wiley, New York (in press) (c) Pross A (1985) Acc Chem Res 18: 212 (d) Pross A, Chipman DM (1987) Free Radical Biology&Medicine 3: 55CrossRefGoogle Scholar
  6. 6.
    Shusterman AJ, Tamir I, Pross A (1988) J Organomet Chem 340: 203CrossRefGoogle Scholar
  7. 7.
    Shaik SS, Hiberty PC, Ohanessian G, Lefour JM (1988) J Phys Chem 92: 5086CrossRefGoogle Scholar
  8. 8.
    Shaik SS (1989) In: Bertran J, Csizmadia IG (Ed) New concepts for understanding organic reactions, Kluwer, Dordrecht: NATO ASI series Vol. C267Google Scholar
  9. 9.
    Lowry TH, Richardson KS (1987) Mechanism and theory in organic chemistry, Harper and Row, New York, p 604–608; 359-360Google Scholar
  10. 10.
    Eberson L (1987) Electron transfer in organic chemistry, Springer-Verlag, BerlinCrossRefGoogle Scholar
  11. 11.(a)
    Hiberty PC, Lefour JM (1987) J Chim Phys 84: 607 (b) Maitre P, Lefour JM, Ohanessian G, Hiberty PC (1990) J Phys Chem 94: 4082 (c) Lefour JM, Flament JP (1984 9) A multi structure VB program, D.C.M.R., Ecole Polytechnique, 91128, Paleseau Cedex, FranceGoogle Scholar
  12. 12.(a)
    Sini G, Shaik SS, Lefour JM, Ohanessian G, Hiberty PC (1989) J Phys Chem 93: 5661 (b) Sini G, Hiberty PC, Shaik SS (1989) J Chem Soc Chem Commun 772 (c) Sini G, Ohanessian G, Hiberty PC, Shaik SS (1990) J Am Chem Soc 112: 1407 (d) Maitre P, Hiberty PC, Ohanessian G, Shaik SS (1990) J Phys Chem 94: 4089CrossRefGoogle Scholar
  13. 13.
    McWeeny R, Sutcliffe BT (1969) Methods of molecular quantum mechanics, Academic Press, London, 1969, Chap 6Google Scholar
  14. 14.
    Lewis GN (1916) J Am Chem Soc 38: 762CrossRefGoogle Scholar
  15. 15.
    Pauling L (1939) The nature of the chemical bond, Cornell Univ Press, Ithaca, 1939Google Scholar
  16. 16.
    Sanderson RT (1983) Polar covalence, Academic Press, New YorkGoogle Scholar
  17. 17.
    Hiberty PC, Cooper DL (1988) J Mol Struct (THEOCHEM) 1969: 437CrossRefGoogle Scholar
  18. 18.(a)
    Karafiloglou P, Malrieu JP (1986) Chem Phys 104: 383 (b) Lepetit MB, Oujia, B, Malrieu JP, Maynau D (1989) Phys Rev A 39: 3274, 3289CrossRefGoogle Scholar
  19. 19.(a)
    Epiotis ND (1982) Lecture Notes Chem 30: 1–260 (b) Epiotis ND (1983) Lecture Notes Chem 34: 1-585CrossRefGoogle Scholar
  20. 20.(a)
    Hiberty PC, Leforestier C (1978) J Am Chem Soc 100: 2012 (b) Hiberty PC (1981) Int J Quant Chem XIX: 259CrossRefGoogle Scholar
  21. 21.
    Harcourt RD (1982) Lecture Notes Chem 30: 1–260 (especially chapter 23)CrossRefGoogle Scholar
  22. 22.(a)
    Hirst DM, Linnett JW (1962) J Chem Soc 1035 (b) Hirst DM, Linnett JW (1963) J Chem Soc 1068Google Scholar
  23. 23.
    Coulson CA, Fischer I (1949) Phil Magasine 49: 386Google Scholar
  24. 24.
    Bobrowicz FB, Goddard WA, III (1977) In: Schaefer HF (Ed) Methods of electronic structure theory, Plenum, New York, p 79CrossRefGoogle Scholar
  25. 25.
    Cooper DL, Gerratt J, Raimondi M (1987) Adv Chem Phys 69: 319Google Scholar
  26. 26.
    Shaik SS, Bar R (1984) New J Chem 8: 411Google Scholar
  27. 27.
    Shaik SS, Hiberty PC, Ohanessian G, Lefour JM (1985) New J Chem 9: 385Google Scholar
  28. 28.
    Kabbaj OK, Volatron F, Malrieu JP (1988) Chem Phys Lett 147: 353CrossRefGoogle Scholar
  29. 29.
    Buncel E, Urn IH, Shaik SS, Wolfe S (1988) J Am Chem Soc 110: 1275CrossRefGoogle Scholar
  30. 30.
    Kochi JK (1988) Angew Chem Int Ed Engl 27: 1227CrossRefGoogle Scholar
  31. 31.
    Shaik SS (1987) J Org Chem 52: 1563CrossRefGoogle Scholar
  32. 32.(a)
    Shaik SS (1982) New J Chem 6: 159 (b) Shaik SS, Pross A (1982) J Am Chem Soc 104:2708Google Scholar
  33. 33.
    Bell RP (1936) Proc R Soc London A 154: 414CrossRefGoogle Scholar
  34. 34.
    Bronsted JN (1928) Chem Rev 5: 231CrossRefGoogle Scholar
  35. 35.
    Shaik SS, Duzy E, Bartuv A (1990) J Phys Chem 94: 6574CrossRefGoogle Scholar
  36. 36.
    Malrieu JP (1986) New J Chem 10: 61Google Scholar
  37. 37.
    Woodward RB, Hoffmann R (1970) The conservation of orbital symmetry, Academic Press, New York, 1970Google Scholar
  38. 38.
    Kabbaj OK, Sini G, Hiberty PC, to be publishedGoogle Scholar
  39. 39.
    Cohen D, Bar R, Shaik SS (1986) J Am Chem Soc 108: 231CrossRefGoogle Scholar
  40. 40.
    Demolliens A, Eisenstein O, Hiberty PC, Lefour JM, Ohanessian G, Shaik SS, Volatron F (1989) J Am Chem Soc 111: 5623CrossRefGoogle Scholar
  41. 41.(a)
    Pellerite MJ, Brauman JI (1983) J Am Chem Soc 105: 2672 (b) Dodd A, Brauman JI (1984) J Am Chem Soc 106: 5356 (c) Barlow SE, van Doren JM, Bierbaum VM (1988) J Am Chem Soc 110: 7240CrossRefGoogle Scholar
  42. 42.(a)
    Wolfe S, Mitchell DJ, Schlegel HB (1981) J Am Chem Soc 103: 6794 (b) Mitchell DJ (1981) PhD Thesis, Queen’s University, Kingston, Canada (c) Mitchell DJ, Schlegel HB, Shaik SS, Wolfe S (1985) Can J Chem 63: 1642Google Scholar
  43. 43.(a)
    Albery WJ, Kreevoy MM (1978) Adv Phys Org Chem 16: 87 (b) Lewis ES, McLaughlin ML, Douglas TA (1987) In: Harris JM, McManus SP (Eds) Nucleophilicity, American Chemical Society, Washington DCGoogle Scholar
  44. 44.(a)
    Bertran J (1989) In: Bertran J, Csizmadia IG (Eds) New theoretical concepts for understanding chemical reactions, NATO ASI Series, Kluwer, Dordrecht, Vol C267 (b) Bergsma JP, Gertner BJ, Wilson KR, Hynes JT (1987) J Chem Phys 86: 1356 (c) Gertner BJ, Bergsma JP, Wilson KR, Lee S, Hynes JT (1987) J Chem Phys 85: 1377 (d) Hwang JK, King G, Creighton S, Warshel A (1988) J Am Chem Soc 110: 5297 (e) Van Linde SR, Hase WL (1989) J Am Chem Soc 110: 7240CrossRefGoogle Scholar
  45. 45.(a)
    Janousek BK, Brauman JI (1979) In: Bowers MT (Ed) Gas phase ion chemistry. Academic Press, New York, Vol. 2 (b) Chen ECM, Wentworth WE (1975) J Chem Educ 52: 486 (c) Jiordan JC, Moore JH, Tosseil JA (1986) Acc Chem Res 19: 281 (d) Olthoff JK (1985): PhD Dissertation, University of Maryland, USA (e) Lindholm E, Li J (1988) J Phys Chem 92: 1713 (0 Jordan KD, Burrow PD (1987) Chem Rev 67: 557 (g) Heinrich N, Koch W, Frenking G (1986) Chem Phys Lett 124: 20 (h) Luke BT, Loew GH, McLean AD (1988) J Am Chem Soc 110: 3396 (i) Hitchcock AP, Tronc M, Modelli A (1989) J Phys Chem 93: 3068Google Scholar
  46. 46.
    Shaik SS (1983) J Am Chem Soc 105: 4359CrossRefGoogle Scholar
  47. 47.(a)
    Tucker SC, Truhlar DG (1989) J Phys Chem 93: 8138 (b) Chandrasekhar J, Smith SF, Jorgensen WL (1985) J Am Chem Soc 107: 154CrossRefGoogle Scholar
  48. 48.
    Dewar MJS, Healy E (1982) Organometallics 1: 1705CrossRefGoogle Scholar
  49. 49.
    Shaik SS, Schlegel HB, Wolfe S (1988) J Chem Soc Chem Commun 1322Google Scholar
  50. 50.(a)
    Sini G (1991) PhD Dissertation, Universite de paris Sud, Orsay, France (b) Kabbaj OK (1989) DEA Thesis, Universite Paul Sabatier, Toulouse, and Universite de paris Sud, Orsay, FranceGoogle Scholar
  51. 51.(a)
    Tedder JM Walton JC (1978) Adv Phys Org Chem 16: 51 (b) Tedder JM, Walton JC (1980) Tetrahedron 36: 701 (c) Tedder JM (1982) Angew Chem Int Ed Engl 21: 401Google Scholar
  52. 52.
    Shaik SS, Canadell E (1990) J Am Chem Soc 112: 1446CrossRefGoogle Scholar
  53. 53.
    Kitaura K, Morokuma K (1976) Int J Quant Chem 10: 325CrossRefGoogle Scholar
  54. 54.(a)
    Wu EC, Rodgers AS (1976) 98: 6112 (b) Kerr JA, Parsonage MJ, Trotman-Dickenson AF (1976) In: The handbook of chemistry and physics, CRC Press, Cleaveland, OH, p F-204-F-220Google Scholar
  55. 55.
    Canadell E, Eisenstein O, Ohanessian G, Poblet JM (1985) J Phys Chem 89: 4856CrossRefGoogle Scholar
  56. 56.(a)
    Houk KN, Gandour RW, Strozier RW, Rondan NG, Paquette LA (1979) J Am Chem Soc 101: 6797 (b) Bach RD, Wolber GJ, Schlegel HB (1985) J Am Chem Soc 107: 2837CrossRefGoogle Scholar
  57. 57.(a)
    Boal DH, Ozin GA (1971) J Chem Phys 55: 3598 (b) Nelson LY, Pimentel GC (1967) J Chem Phys 47: 3671 (c) Lee YT, Lebreton PR, McDonald JD, Herschbach DR (1969) J Chem Phys 51: 455CrossRefGoogle Scholar
  58. 58.
    Shaik SS, Hiberty PC, Lefour JM, Ohanessian G (1987) J Am Chem Soc 109: 363CrossRefGoogle Scholar
  59. 59.(a)
    Malrieu JP, Maynau D, Daudey JP (1984) Phys Rev B 30: 1817 (b) Durand P, Malrieu JP (1987) Adv Chem Phys 67: 321CrossRefGoogle Scholar
  60. 60.
    Epiotis ND (1984) New J Chem 8: 11Google Scholar
  61. 61.
    Schleyer PvR, Martin JC (1984) Chem Eng News May 28: 4Google Scholar
  62. 62.(a)
    Musher JI (1969) Angew Chem Int Ed Engl 8: 54 (b) Kutzelnigg W (1984) Angew Chem Int Ed Engl 23: 272 (c) Coulson CA (1969) Nature 221: 1106 (d) Martin JC (1983) Science 221: 509CrossRefGoogle Scholar
  63. 63.(a)
    McDowell CA, Mitchell KAR, Raghunathan P (1972) J Chem Phys 57: 1699 (b) Clakton TA, Fullam BW, Platt E, Symons MCR (1975) J Chem Soc Dalton Trans 1395 (c) Colussi AJ, Morton JR, Preston KF ( 1975) J Chem Phys 62: 2004; J Phys Chem 79: 1855CrossRefGoogle Scholar
  64. 64.
    Nakamura K, Masaki N, Sato S, Shimokoshi K (1985) J Chem Phys 83: 4504CrossRefGoogle Scholar
  65. 65.(a)
    Volatron F, Maitre P, Pelissier M (1990) Chem Phys Lett 166: 49 (b) Volatron F, Demolliens A, Lefour JM, Eisenstein O (1986) Chem Phys Lett 130: 419CrossRefGoogle Scholar
  66. 66.(a)
    For H2S: Turner DW, Baker C, Baker AD, Brundle CR (1970) Molecular photoelectron spectroscopy, Wiley, London (b) For PH3: Bowers MT (Ed) Gas phase ion chemistry (1979), Academic Press, New York, Vol 2, p 17Google Scholar
  67. 67.
    Hiberty PC, Ohanessian G (1982) J Am Chem Soc 104: 66CrossRefGoogle Scholar
  68. 68.
    Katz B, personal communication to Shaik SSGoogle Scholar
  69. 69.
    Kassab E, Evleth EM (1987) J Am Chem Soc 109: 1653CrossRefGoogle Scholar
  70. 70.
    Hajdasz DJ, Squires RR (1986) J Am Chem Soc 108: 3139CrossRefGoogle Scholar
  71. 71.
    Reed AE, Schleyer PvR (1987) Chem Phys Lett 133: 553CrossRefGoogle Scholar
  72. 72.
    Marcus RA (1964) Annu Rev Phys Chem 15: 155CrossRefGoogle Scholar
  73. 73.
    Longuet-Higgins HC, Abrahamson EW (1965) J Am Chem Soc 87: 2045CrossRefGoogle Scholar
  74. 74.
    Salem L (1976) Science 191: 822CrossRefGoogle Scholar
  75. 75.
    Devaquet A, Sevin A, Bigot B (1978) J Am Chem Soc 100: 2009CrossRefGoogle Scholar
  76. 76.
    Robb MA, Bernardi F (1989) In: Bertran J, Csizmadia IG (Ed) New concepts for understanding organic reactions, Kluwer, Dordrecht: NATO ASI series Vol C267Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1991

Authors and Affiliations

  • Sason S. Shaik
    • 1
  • Philippe C. Hiberty
    • 2
  1. 1.Department of ChemistryBen Gurion UniversityBecr-ShevaIsrael
  2. 2.Laboratoire de Chimie Théorique, Bât. 490Université de Paris-SudOrsay CedexFrance

Personalised recommendations