π bonding in second and third row molecules: Testing the strength of Linus's blanket

Chemistry - A European Journal

Volumn 6, Issue 13, 2000, Pages 2425-2434

  Galbraith, John Morrison ^a   Blank, Esti ^a   Shaik, Sason ^a   Hiberty, Philippe C ^b  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b UNIVERSITÉ PARIS SACLAY   (France)

Author keywords

Ab initio calculations; Bond theory; Charge shift bonds; Valence bond; interactions

Indexed keywords

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL STRUCTURE; COVALENT BOND; MOLECULAR INTERACTION; THEORY; THERMODYNAMICS;

EID: 0034600910     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20000703)6:13<2425::AID-CHEM2425>3.0.CO;2-0     Document Type: Article

References (59)

1. a) S. Shaik, A. Shurki, Angew. Chem. 1999, 111, 616; Angew. Chem. Int. Ed. 1999, 38, 586;
2. a) S. Shaik, A. Shurki, Angew. Chem. 1999, 111, 616; Angew. Chem. Int. Ed. 1999, 38, 586;
3. b) P. C. Hiberty, J. Mol. Struct. (THEOCHEM) 1998, 451, 237;
4. c) D. J. Klein, H. Zhu, R. Valenti, M. A. Garcia-Bach, Int. J. Quant. Chem. 1997, 65, 421;
5. d) D. L. Cooper, J. Gerratt, M. Raimondi, Chem. Rev. 1991, 91, 927;
6. e) J. Gerratt, D. L. Cooper, P. B. Karadakov, M. Raimondi, Chem. Soc. Rev. 1997, 87.
7. L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell University Press, Ithaca, 1960.
8. See Ref. [2], p. 80.
9. L. Pauling, J. Sherman, J. Am. Chem. Soc. 1937, 59, 1450.
10. See Ref. [2], p. 93.
11. H. M. Rosenstock, K. Draxl, B. W. Steiner, J. T. Heron, J. Phys. Chem. Ref. Data 1977, 6, Supplement 1.
12. a) E. A. Carter, W. A. Goddard, J. Chem. Phys. 1988, 88, 1752;
13. b) E. A. Carter, W. A. Goddard, J. Phys. Chem. 1986, 90, 998.
14. M. Karni, Y. Apeloig, J. Am. Chem. Soc. 1990, 112, 8589.
15. M. W. Schmidt, P. N. Truong, M. S. Gordon, J. Am. Chem. Soc. 1987, 109, 5217.
16. It is not possible to place two singlet paired electrons in overlapping p-type atomic orbitals without creating a bond.
17. P. von R. Schleyer, D. Kost, J. Am. Chem. Soc. 1988, 110, 2105.
18. W. Kutzelnigg, Angew. Chem. 1984, 96, 262; Angew. Chem. Int. Ed. Engl. 1984, 23, 272.
19. W. Kutzelnigg, Angew. Chem. 1984, 96, 262; Angew. Chem. Int. Ed. Engl. 1984, 23, 272.
20. J. Verbeek, J. H. Langenberg, C. P. Byrman, J. H. van Lenthe, TURTLE -ab initio VB/VBSCF/VBCI program; Theoretical Chemistry group, Debye Institute, University of Utrecht, 1993.
21. a) A. Banerjee, F. Grein, Int. J. Quant. Chem. 1976, 10, 123;
22. b) F. Grein, T. C. Chang, Chem. Phys. Lett. 1971, 12, 44.
23. B. Levy, G. Berthier, Int. J. Quant. Chem. 1968, 2, 307.
24. a) D. Lauvergnat, P. C. Hiberty, D. Danovich, S. Shaik, J. Phys. Chem. 1996, 100, 5715;
25. b) P. C. Hiberty, C. P. Byrman, J. Am. Chem. Soc. 1995, 117, 9875;
26. c) P. C. Hiberty, S. Humbel, C. P. Byrman, J. van Lenthe, J. Chem. Phys. 1994, 101, 5969;
27. d) P. C. Hiberty, S. Humbel, P. Archirel, J. Phys. Chem. 1994, 98, 11697;
28. e) P. C. Hiberty, J. P. Flament, E. Noizet, Chem. Phys. Lett. 1992, 189, 259.
29. P. C. Hiberty, D. Danovich, A. Shurki, S. Shaik, J. Am. Chem. Soc. 1995, 117, 7760.
30. F. W. Bobrowicz, W. A. Goddard in Modern Theoretical Chemistry: Methods of Electronic Structure Theory, Vol. 3 (Ed.: H. F. Schaefer), Plenum, New York, 1977, p. 79.
31. a) P. C. Hiberty, J. Mol. Struct. (THEOCHEM) 1998, 451, 237;
32. b) P. C. Hiberty, D. L. Cooper, J. Mol. Struct. (THEOCHEM) 1988, 169, 437.
33. Note that the above basis set dependency problem only concerns VB structures that are calculated alone. On the other hand, no problem of this kind is encountered in the calculation of the BOVB ground state. The BOVB wave functions, and their associated properties (bonding energies, optimized geometries, weights of covalent vs ionic structures, etc.) are not basis set dependent.
34. S. Shaik, in New Theoretical Concepts for Understanding Organic Reactions, Vol. C267 (Eds.: J. Bertrán, I. G. Csizmadia), Kluwer, Dordrecht, 1989, p. 165.
35. H. B. Chirgwin, C. A. Coulson, Proc. R. Soc. London, Ser. A 1950, 2, 196.
36. P. Hohenberg, W. Kohn, Phys. Rev. B 1964, 136, 864;
37. b) W. Kohn, L. J. Sham, Phys. Rev. A 1965, 140, 1133.
38. a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648;
39. b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785;
40. c) B. Miehlich, A. Savin, H. Stoll, H. Preuss, Chem. Phys. Lett. 1989, 157, 200.
41. J. S. Krishnan, R. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650.
42. A. D. MacLean, G. S. Chandler, J. Chem. Phys. 1980, 72, 5639.
43. H. Jacobsen, T. Ziegler, J. Am. Chem. Soc. 1994, 116, 3667.
44. B. O. Roos, Adv. Chem. Phys. 1987, 69, 399.
45. 1Δ for O=S) for the geometries of O=O, S=S and O=S.
46. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople, GAUSSIAN94, Revision D.4, GAUSSIAN, Inc., Pittsburgh PA, 1995.
47. a) A. Shurki, P. C. Hiberty, S. Shaik, J. Am Chem. Soc. 1999, 121, 822;
48. b) D. Lauvergnat, P. Maître, P. C. Hiberty, F. Volatron, J. Phys. Chem. 1996, 100, 6463;
49. c) G. Sini, P. Maître, P. C. Hiberty, S. Shaik, J. Mol. Struct. (THEOCHEM) 1991, 229, 163;
50. d) R. T. Sanderson, Polar Covalence, Academic Press, New York, 1983.
51. Use of the geometric mean instead of the arithmetic mean does not change these results and therefore a plot of Dπ vs. the geometric mean is not shown herein.
52. 2.
53. S. Shaik, P. Maitre, G. Sini, P. C. Hiberty, J. Am. Chem. Soc. 1992, 114, 7861.
54. a) W. Kutzelnigg, in Theoretical Models for Chemical Bonding, Vol. 2 (Ed.: Z.B. Maksic), Springer, Heidelberg, 1990;
55. b) W. C. Wilson, W. A. Goddard, Theoret. Chim. Acta 1972, 26, 195, 211;
56. c) M. J. Feinberg, K. Ruedenberg, Adv. Quant. Chem. 1970, 5, 27;
57. d) O. V. Gritsenko, E. J. Baerends, Theor. Chem. Acc. 1997 96, 44.
58. VBSCF values correlate with the electronegativity sum as in Figure 3. Furthermore, the RE increments from VBSCF to BOVB also correlate with the electronegativity sum. The uniformity of these trends is an indication of their reliability.
59. F. Weinhold, Conference Proceedings: Frontiers in Electronic Structure Calculations, Haifa, 1998, private communication.