Reliability of hybrid density theory—semiempirical approach for evaluation of bond dissociation energies

Abstract

The various bond dissociation energies for organic molecules are computed with the hybrid B3LYP/6-31G(d) theory model on AM1 energies. This approach computes bond dissociation energies that are very similar to full B3LYP/6-31G(d) computed values, which are, on the other hand, 5–10 kcal mol^–1 away from the experimental values. If correction factors are applied, very good agreement with the experiment can be obtained. This approach is designed to evaluate bond dissociation energies on large molecular systems with a modest computational requirement.

References

1. W. J. Hehre, L. D. Burke, A. J. Shusterman and W. J. Pietro, Experiments in Computational Organic Chemistry, Wavefunction, Inc., Irvine, California, 1993.
2. T. Clark, A Handbook of Computational Chemistry, Wiley, New York, NY, 1986.
3. S. S. Shaik, H. B. Schlegel and S. Wolfe, Theoretical Aspects of Physical Organic Chemistry, Wiley, New York, NY, 1992.
4. L. Salem, Electrons in Chemical Reactions: First Principles, Wiley, New York, NY, 1982.
5. C. Párkányi, Editor, Theoretical Organic Chemistry, Elsevier, Amsterdam, 1998.
6. For instance see: T. J. Lee, E. Rice, G. E. Scuseria and H. F. Schaefer, Theor. Chim. Acta, 1989, 75, 81 and references therein.
7. J. K. Labanowski and J. W. Andzelm, Density Functional Methods in Chemistry, Springer-Verlag, New York, NY, 1991.
8. J. M. Seminario, P. Politzer, Editors, and Modern Density Functional Theory: A Tool for Chemistry, Elsevier, Amsterdam, 1995.
9. J. M. Seminario, Editor, Recent Developments and Applications of Modern Density Functional Theory, Elsevier, Amsterdam, 1996.
10. R. G. Parr and W. Yang, Density-Functional Theory of Atoms and Molecules, Oxford University, Oxford, 1989.
11. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1995, 358, 145.
12. B. S. Jursic and Z. Zdravkovski, Int. J. Quantum Chem., 1995, 54, 161.
13. B. S. Jursic, Chem. Phys. Lett., 1995, 236, 206.
14. B. S. Jursic, Int. J. Quantum Chem., 1996, 57, 213.
15. B. S. Jursic, Int. J. Quantum Chem., 1996, 58, 41.
16. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 365, 47.
17. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 366, 97.
18. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1997, 389, 75.
19. B. S. Jursic, Int. J. Quantum Chem., 1997, 62, 515.
20. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1997, 389, 251.
21. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1997, 418, 165.
22. B. S. Jursic, Computing Transition State Structures with Density Functional Theory Methods, in Recent Developments and Applications of Modern Density Functional Theory, J. H. Seminario, Editor, Elsevier, Amsterdam, 1996, pp. 709–742.
23. B. S. Jursic, Exploring Reaction Outcomes Through the Reactivity-Selectivity Principle Estimated by Density Functional Theory Studies, in Computational Organic Chemistry, C. Párkànyi, Editor, Elsevier, Amsterdam, 1998, pp. 95–133.
24. B. S. Jursic, Cycloaddition Reactions Involving Heterocyclic Compounds as Synthons in the Preparation of Valuable Organic Compounds. An Effective Combination of a Computational Study and Synthetic Applications of Heterocycle Transformations, in Computational Organic Chemistry, C. Prknyi, Editor, Elsevier, Amsterdam, 1998, pp. 501–579.
25. B. S. Jursic and Z. Zdravkovski, J. Chem. Soc., Perkin Trans. 2, 1995, 1223.
26. B. S. Jursic and Z. Zdravkovski, Int. J. Quantum Chem., 1995, 56, 115.
27. B. S. Jursic, Chem. Phys. Lett., 1995, 244, 263.
28. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1995, 357, 243.
29. B. S. Jursic, J. Org. Chem., 1995, 60, 4721.
30. B. S. Jursic, J. Chem. Soc., Perkin Trans. 2, 1996, 1021.
31. B. S. Jursic, Chem. Phys. Lett., 1996, 256, 213.
32. B. S. Jursic, Chem. Phys. Lett., 1996, 256, 603.
33. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 365, 75.
34. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 366, 109.
35. B. S. Jursic, Chem. Phys. Lett., 1996, 261, 13.
36. B. S. Jursic, J. Chem. Soc., Faraday Trans., 1996, 92, 3467.
37. B. S. Jursic, Chem. Phys. Lett., 1997, 264, 113.
38. B. S. Jursic, J. Phys. Chem. A, 1997, 101, 2345.
39. B. S. Jursic, J. Chem. Soc., Perkin Trans. 2, 1997, 637.
40. B. S. Jursic, Int. J. Quantum Chem., 1997, 62, 639.
41. B. S. Jursic, J. Org. Chem., 1997, 67, 3046.
42. B. S. Jursic, J. Chem. Soc., Faraday Trans., 1997, 93, 2355.
43. B. S. Jursic, Int. J. Quantum Chem., 1998, 66, 409.
44. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1998, 423, 189.
45. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1998, 427, 137.
46. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1998, 430, 17.
47. B. S. Jursic, J. Comput. Chem., 1996, 17, 835.
48. B. S. Jursic, Chem. Phys., 1997, 219, 57.
49. B. S. Jursic, L. Klasinc, S. Pecur and W. A. Pryor, Nitric Oxide: Biology and Chemistry, 1997, 1, 494.
50. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1998, 428, 61.
51. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1998, 428, 175.
52. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1997, 394, 15.
53. B. S. Jursic, Int. J. Quant. Chem., 1997, 64, 263.
54. B. S. Jursic and R. Martin, Int. J. Quantum Chem., 1996, 59, 495.
55. B. S. Jursic, J. W. Timberlake and P. S. Engel, Tetrahedron Lett., 1996, 37, 6473.
56. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 366, 103.
57. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 370, 65.
58. B. S. Jursic, Int. J. Quantum Chem., 1997, 62, 291.
59. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1998, 422, 253.
60. H. B. Schlegel and M. J. Frish, Computational Bottlenecks in Molecular Orbital Calculations, in Theoretical and Computational Methods in Organic Chemsitry, S. J. Formosinho, Editor, Kluwer Academic Publs., The Netherlands, NATO-ASI Series C 339, 1991, pp. 5–33.
61. J. A. Pople, M. Head-Gordon, D. J. Fox, K. Raghavachari and L. A. Curtiss, J. Chem. Phys., 1989, 90, 5622.
62. L. A. Curtiss, K. Raghavachari, G. W. Trucks and J. A. Pople, J. Chem. Phys., 1991, 94, 7221.
63. D. K. Malick and G. A. Petersson, J. Chem. Phys., 1998, 108, 5704 and references therein.
64. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1995, 358, 139.
65. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 365, 55.
66. B. S. Jursic and B. LeBlanc, J. Heterocycl. Chem., 1996, 33, 1389.
67. B. S. Jursic, J. Mol. Struct. (THEOCHEM), 1996, 370, 85.
68. B. S. Jursic, J. Heterocycl. Chem., 1977, 34, 1383.
69. M. J. S. Dewar, E. G. Zoebisch, E. F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 1985, 107, 3902.
70. A. D. Becke, J. Chem. Phys., 1993, 98, 1372.
71. C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785.
72. For comparison of the transition state structures computed at various theory level see: K. N. Houk, Y. Li and J. D. Evanseck, Angew. Chem., Int. Ed. Engl., 1992, 21, 682.
73. For instance, see: F. A. Carroll, Perspectives on Structure and Mechanism in Organic Chemistry, Brooks/Cole, Pacific Grove, California, 1998.
74. J. J. P. Stewart, MOPAC60, QCPE No. 455, Indiana University, Bloomington, 1983.
75. M. J. Frisch, J. A. Pople and J. S. Binkley, J. Chem. Phys., 1984, 80, 3265.
76. Gaussian 94, Revision B. 3, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. 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, 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 and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
77. W. J. Hehre, L. Radom, P. v. R. Schleyer and J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986.
78. All experimental values are taken from CRC Handbook of Chemistry and Physics, 67th Edition, CRC Press, Boca Raton, Florida, 1987, F-178.