Energy component analysis of the pseudo-Jahn-Teller effect in the ground state of the triafulvalene anion, pentafulvalene cation, and heptafulvalene anion radicals

Journal of Physical Chemistry A

Volumn 102, Issue 2, 1998, Pages 490-495

  Toyota, Azumao ^a   Koseki, Shiro ^b  

^a YAMAGATA UNIVERSITY   (Japan)

^b MIE UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC HYDROCARBONS; ELECTRON ENERGY LEVELS; ELECTRONIC DENSITY OF STATES; ELECTRONIC PROPERTIES; ELECTRONIC STRUCTURE; IONS;

HEPTAFULVALENE ANION; MOLECULAR SKELETON; PENTAFULVALENE CATION; PSEUDO-JAHN-TELLER EFFECT; SPIN DENSITY DISTRIBUTION; TRIAFULVALENE ANION;

MOLECULAR STRUCTURE;

EID: 0032495413     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp972858p     Document Type: Article

References (45)

1. John. H. A.; Teller, E. Proc. R. Soc. London 1937, A161, 220.
2. Salem, L. The Molecular Orbital Theory of Conjugated Systems; Benjamin: New York, 1966, and references therein.
3. Englman, R. The Jahn-Teller Effect in Molecules and Crystals; Wiley: London, 1972.
4. Pearson, R. G. Symmetry Rules for Chemical Reactions; Wiley: New York, 1976.
5. Legoff, E. J. Am. Chem. Soc. 1962, 84, 3975.
6. Bloch, R.; Marty, R. A.; de Mayo, P. J. Am. Chem. Soc. 1971, 93, 3071.
7. Hafner, K. Pure Appl. Chem. 1982, 54, 939.
8. Hafner, K.; Süss, H. U. Angew. Chem., Int. Ed. Engl. 1973, 12, 575.
9. Dauben, H. J.; Bertelli, D. J. J. Am. Chem. Soc. 1961, 83, 4657.
10. Vogel, E.; Konigshofen, H.; Wassen, J.; Mullen, K.; Oth, J. F. M. Angew. Chem., Int. Ed. Engl. 1974, 13, 732.
11. Linder, H. J.; Kitschuke, B. Angew. Chem., Int. Ed. Engl. 1976, 15, 106.
12. Stegemann, J.; Linder, H. J. Tetrahedron Lett. 1977, 29, 2515.
13. Gleiter, R.; Bischof, P. In Topics in Nonbenzenoid Aromatic Chemistry, Hirokawa Publishing Co.: Tokyo, 1977; Vol. 2, p 1.
14. Stowasser, B.; Hafner, K. Angew. Chem., Int. Ed. Engl. 1986, 25, 466.
15. (a) Doering, W. v. E. Theoretical Organic Chemistry; Academic Press: New York, 1959; p 35.
16. (b) Escher, A.; Rutsch, W.; Neuenschwander, M. Helv. Chim. Acta 1986, 69, 1644.
17. Sevilla, M. D.; Flajer, S. H.; Vincov, G.; Dauben, H. J. Jr. J. Am. Chem. Soc. 1969, 91, 4139.
18. Bauld, N. L.; Chang, C. S.; Eilert, J. H. Tetrahedron Lett. 1973, 153.
19. Jackman, L. M.; Sondheimer, F.; Amiel, Y.; Ben-Efraim, D. A.; Gerona, Y.; Wolovsky, R.; Bothner-By, A. A. J. Am. Chem. Soc. 1962, 87, 4307.
20. Sondheimer, F.; Wolovsky, R.; Amiel, Y. J. Am. Chem. Soc. 1965, 87, 3253.
21. Toyota, A.; Koseki, S. J. Phys. Chem. 1996, 100, 2100.
22. Koseki, S.; Toyota, A. J. Phys. Chem. 1997, 101, 5712.
23. Schmidt, M. W.; Baldrige, K. K.; Boats, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S.; Windus, T. L.; Dupuis, M.; Montgomery Jr., J. A. J. Comput. Chem. 1993, 14, 1347.
24. Ditchfield, E.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724.
25. Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
26. Ruedenberg, K.; Schmidt, M. W.; Dombek, M. M.; Elbert, S. T. Chem. Phys. 1982, 71, 41-49, 51-64, 65-78.
27. The d exponent was 0.8 for carbon atoms.
28. Neidlein, R.; Poignee', V.; Kramer, W.; Gluck, C. Angew. Chem., Int. Ed. Engl. 1986, 25, 731.
29. Agranat, I. Org. Mass Spectrom. 1973, 7, 907.
30. Davies, A. G.; Giles, J. R. M.; Lusztyk, J. J. Chem. Soc., Perkin Trans. 2 1981, 747.
31. Ichikawa, H.; Ebisawa, Y. J. Am. Chem. Soc. 1985, 107, 1161.
32. (a) See, however, the X-ray study on the neutral heptafulvalene molecule: Thomas, R.; Coppens, P. Acta Crystallogr. 1972, B28, 1800.
33. (b) For a recent interesting theoretical study on the molecule, see also: Scott, A. P.; Agranat, I.; Biedermann, P. U.; Riggs, N. V.; Radom, L. J. Org. Chem. 1997, 62, 2026.
34. Nakajima, T.; Toyota, A.; S. Fujii, Bull. Chem. Soc. Jpn. 1972, 45, 1022, and references therein.
35. Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833, 1841, 2338, 2343.
36. Toyota, A.; Saito, M.; Nakajima, T. Theor. Chim. Acta 1980, 56, 231, and references cited therein.
37. 22
38. In ref 34, a localization of the unpaired spin density in the radicals 2 and 3 has been accounted for in terms of the broken-symmetry charge density wave arising from the doublet instability of the RHF solution. For a similar study, see also: Toyota, A.: Nakajima, T. Theor. Chim. Acta 1982, 61, 505.
39. Boyd, R. J.; Darvesh, K.; Fricker, P. D. J. Chem. Phys. 1991, 94, 8083.
40. Wang, J.; Boyd, R. J. J. Chem. Phys. 1992, 96, 1232.
41. Baur, W. H. Acta Crystallogr. 1972, B28, 1456.
42. Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY, 1960; Chapter 7.
43. However, the X-ray study on tetra-tert-butylcyclobutadiene at -150 °C indicates that the nonbonded atomic distances between hydrogen atoms are in the range of 1.77-1.98: Imgartinger, H.; Nixdorf, M. Angew. Chem., Int. Ed. Engl. 1983, 22, 403.
44. Toyota, A.; Koseki, S. Unpublished work.
45. Ichikawa, H.; Kagawa, H. J. Phys. Chem. 1995, 99, 2307.