The C4H4·+ potential energy surface. 2. The Jahn-Teller stabilization of ionized tetrahedrane and its rearrangement to cyclobutadiene radical cation

Journal of Physical Chemistry A

Volumn 101, Issue 21, 1997, Pages 3918-3924

  Hrouda, Vojtěch ^a,b   Bally, Thomas ^a   Čársky, Petr ^b   Jungwirth, Pavel ^b  

^a UNIVERSITY OF FRIBOURG   (Switzerland)

^b J HEYROVSKÝ INSTITUTE OF PHYSICAL CHEMISTRY   (Czech Republic)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001308554     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp962287l     Document Type: Article

References (55)

1. Part 1: Roeselová, M.; Bally, T.; Jungwirth, P.; Čársky, P. Chem. Phys. Lett. 1995, 234, 395.
2. Maier, G. Angew. Chem. 1988, 100, 317; Angew. Chem., Int. Ed. Engl 1988, 27, 309.
3. Maier, G. Angew. Chem. 1988, 100, 317; Angew. Chem., Int. Ed. Engl 1988, 27, 309.
4. 3 (Maier, G.; Born, B. Angew. Chem. 1989, 101, 1085; Angew. Chem., Int. Ed. Engl. 1989, 28, 1050), and two where the fourth substituent is adamantyl or isopropyl (Maier, G.; Fleischer, F.; Kalinowski, H.-O. Liebigs Ann. 1995, 173).
5. 3 (Maier, G.; Born, B. Angew. Chem. 1989, 101, 1085; Angew. Chem., Int. Ed. Engl. 1989, 28, 1050), and two where the fourth substituent is adamantyl or isopropyl (Maier, G.; Fleischer, F.; Kalinowski, H.-O. Liebigs Ann. 1995, 173).
6. 3 (Maier, G.; Born, B. Angew. Chem. 1989, 101, 1085; Angew. Chem., Int. Ed. Engl. 1989, 28, 1050), and two where the fourth substituent is adamantyl or isopropyl (Maier, G.; Fleischer, F.; Kalinowski, H.-O. Liebigs Ann. 1995, 173).
7. 3 (Maier, G.; Born, B. Angew. Chem. 1989, 101, 1085; Angew. Chem., Int. Ed. Engl. 1989, 28, 1050), and two where the fourth substituent is adamantyl or isopropyl (Maier, G.; Fleischer, F.; Kalinowski, H.-O. Liebigs Ann. 1995, 173).
8. 3 (Maier, G.; Born, B. Angew. Chem. 1989, 101, 1085; Angew. Chem., Int. Ed. Engl. 1989, 28, 1050), and two where the fourth substituent is adamantyl or isopropyl (Maier, G.; Fleischer, F.; Kalinowski, H.-O. Liebigs Ann. 1995, 173).
9. Unsuccessful attempts to prepare parent TH are summarized in ref 2.
10. d to the (chiral) T symmetry was predicted (Hounshell, W. D.; Mislow, K. Tetrahedron Lett. 1979, 1205) and confirmed by MNDO (Schweig, A.; Thiel, W. J. Am. Chem. Soc. 1979, 101, 4742) and may be responsible for the large vibrational ellipsoids of the methyl carbons in the crystal structure (Irngartinger, H.; Goldmann, A.; Jahn, R.; Nixdorf, M.; Rodewald, H.; Maier, G.; Malsch, K.-D.; Emrich, R. Angew. Chem. 1984, 96, 967; Angew. Chem., Int. Ed. Engl. 1984, 23, 993).
11. d to the (chiral) T symmetry was predicted (Hounshell, W. D.; Mislow, K. Tetrahedron Lett. 1979, 1205) and confirmed by MNDO (Schweig, A.; Thiel, W. J. Am. Chem. Soc. 1979, 101, 4742) and may be responsible for the large vibrational ellipsoids of the methyl carbons in the crystal structure (Irngartinger, H.; Goldmann, A.; Jahn, R.; Nixdorf, M.; Rodewald, H.; Maier, G.; Malsch, K.-D.; Emrich, R. Angew. Chem. 1984, 96, 967; Angew. Chem., Int. Ed. Engl. 1984, 23, 993).
12. d to the (chiral) T symmetry was predicted (Hounshell, W. D.; Mislow, K. Tetrahedron Lett. 1979, 1205) and confirmed by MNDO (Schweig, A.; Thiel, W. J. Am. Chem. Soc. 1979, 101, 4742) and may be responsible for the large vibrational ellipsoids of the methyl carbons in the crystal structure (Irngartinger, H.; Goldmann, A.; Jahn, R.; Nixdorf, M.; Rodewald, H.; Maier, G.; Malsch, K.-D.; Emrich, R. Angew. Chem. 1984, 96, 967; Angew. Chem., Int. Ed. Engl. 1984, 23, 993).
13. d to the (chiral) T symmetry was predicted (Hounshell, W. D.; Mislow, K. Tetrahedron Lett. 1979, 1205) and confirmed by MNDO (Schweig, A.; Thiel, W. J. Am. Chem. Soc. 1979, 101, 4742) and may be responsible for the large vibrational ellipsoids of the methyl carbons in the crystal structure (Irngartinger, H.; Goldmann, A.; Jahn, R.; Nixdorf, M.; Rodewald, H.; Maier, G.; Malsch, K.-D.; Emrich, R. Angew. Chem. 1984, 96, 967; Angew. Chem., Int. Ed. Engl. 1984, 23, 993).
14. Bock, H.; Roth B.; Maier, G. Angew. Chem. 1980, 92, 213; Angew. Chem., Int. Ed. Engl. 1980, 19, 209; Chem. Ber. 1984, 177, 172.
15. Bock, H.; Roth B.; Maier, G. Angew. Chem. 1980, 92, 213; Angew. Chem., Int. Ed. Engl. 1980, 19, 209; Chem. Ber. 1984, 177, 172.
16. Bock, H.; Roth B.; Maier, G. Angew. Chem. 1980, 92, 213; Angew. Chem., Int. Ed. Engl. 1980, 19, 209; Chem. Ber. 1984, 177, 172.
17. Fox, M. A.; Campbell, K. A.; Hünig, S.; Berneth, H.; Maier, G.; Schneider, K.-A.; Malsch, K.-D. J. Org. Chem. 1982, 47, 3408.
18. Maier, G.; Raug, H.; Emrich, R.; Gries, S.; Irngartinger, H. Liebigs Ann. 1995, 161.
19. Bally, T. J. Mol. Struct. (THEOCHEM) 1991, 227, 249.
20. For previous work, see: Jungwirth, P.; Čársky, P.; Bally, T. J. Am. Chem. Soc. 1993, 115, 5776. Jungwirth, P.; Bally, T. Ibid. 1993, 115, 5783, and ref I.
21. For previous work, see: Jungwirth, P.; Čársky, P.; Bally, T. J. Am. Chem. Soc. 1993, 115, 5776. Jungwirth, P.; Bally, T. Ibid. 1993, 115, 5783, and ref I.
22. Jungwirth, P.; Čársky, P.; Bally, T. Chem. Phys. Lett. 1992, 195, 371.
23. Bersuker, I. B. The John-Teller Effect and Vibronic Interactions in Modern Chemistry; Plenum Press: New York, 1983.
24. Heilbronner, E.; Jones, T. B.; Krebs, A.; Maier, G.; Maisch, K.-D.; Pocklington, J.; Schmelzer, A. J. Am. Chem. Soc. 1980, 102, 564
25. Coffman, R. E. J. Chem. Phys. 1966, 44, 2305.
26. E| which is obviously independent of φ.
27. This choice is not unambiguous. We could equally well take the separation of the transition state from the conical intersection as a third condition, and then it would be that parameter which is modeled optimally. However, it turns out that in actual fact the choice of one stationary point introduces no big errors in the opposite one.
28. Ceulemans, A.; Beyens, D.; Vanquickenborne, L. G. J. Am. Chem. Soc. 1984, 106, 5824; Ceulemans, A.; Vanquickenborne, L. G. Struct. Bonding 1989, 71, 125.
29. Ceulemans, A.; Beyens, D.; Vanquickenborne, L. G. J. Am. Chem. Soc. 1984, 106, 5824; Ceulemans, A.; Vanquickenborne, L. G. Struct. Bonding 1989, 71, 125.
30. This is a combination of Becke's hybrid gradient corrected exchange functional with three parameters (Becke, A. D. J. Chem. Phys. 1993, 98, 5648), combined with the correlation functional of Lee, Yang, and Parr (Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785). For a description of the density functionals as implemented in the Gaussian series of programs, see: Johnson, B. G.; Gill, P. M. W. L.; Pople, J. A. J. Chem. Phys. 1993, 98, 5612.
31. This is a combination of Becke's hybrid gradient corrected exchange functional with three parameters (Becke, A. D. J. Chem. Phys. 1993, 98, 5648), combined with the correlation functional of Lee, Yang, and Parr (Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785). For a description of the density functionals as implemented in the Gaussian series of programs, see: Johnson, B. G.; Gill, P. M. W. L.; Pople, J. A. J. Chem. Phys. 1993, 98, 5612.
32. This is a combination of Becke's hybrid gradient corrected exchange functional with three parameters (Becke, A. D. J. Chem. Phys. 1993, 98, 5648), combined with the correlation functional of Lee, Yang, and Parr (Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785). For a description of the density functionals as implemented in the Gaussian series of programs, see: Johnson, B. G.; Gill, P. M. W. L.; Pople, J. A. J. Chem. Phys. 1993, 98, 5612.
33. (a) Ziegler, T. Chem. Rev. 1991, 91, 651.
34. (b) Johnson, B. G.; Gill, P. M. W.; Pople, J. A. J. Chem. Phys. 1993, 98, 5612.
35. (c) Handy, N. C.; Murray, C. W.; Amos, R. D. J. Phys. Chem. 1993, 97, 4392.
36. (d) Stephens, B. J.; Devlin, I. J.; Chabalowsky, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
37. (e) Rauhut, G.; Pulay, P. J. Am. Chem. Soc. 1995, 117, 4167; J. Phys. Chem. 1995, 99, 3093.
38. (e) Rauhut, G.; Pulay, P. J. Am. Chem. Soc. 1995, 117, 4167; J. Phys. Chem. 1995, 99, 3093.
39. (f) Bauschlicher, C. W.; Partridge, H. Chem. Phys. Lett. 1995, 240, 533.
40. (g) Martin, J. M. L.; El-Yazal, J.; François, J.-P. Chem. Phys. Lett. 1995, 242, 570.
41. 2〉 values were <0.754 except for rhombic CB (0.770) and the transisition state (0.760).
42. 24
43. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 298, 213.
44. Complete Active Space SCF calculations (see, e.g.: Roos, B. In Lecture Notes in Qauntum Chemistry; Springer: Berlin 1992). This corresponds to a full CI calculation within a limited subset (the "active space") of valence MOs while the MO basis is simultaneously optimized for that CI by varying the AO coefficients. In the present case, the active space included four bonding and four antibonding C-C MOs.
45. Coupled cluster calculation accounting for single and double excitations (see, e.g.: Bartlett, R. J. J. Phys. Chem. 1989, 93, 1697 and references therein ) augmented by a quasi-perturbative estimate for triple excitations (Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479). Extensive applications have shown that this method consistently yields results very close to those obtained by full configuration interaction (cf.: Lee, T. J.; Scuseria, G. E. In Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy; Langhoff, S. R., Ed.; Kluwer: Dordrecht, 1995). Note also, that at this level, the choice of a reference SCF wave fuction (UHF or ROHF) makes no significant difference to the final results (cf. e.g.: Stanton, J. F. J. Chem. Phys. 1994, 191, 371).
46. Coupled cluster calculation accounting for single and double excitations (see, e.g.: Bartlett, R. J. J. Phys. Chem. 1989, 93, 1697 and references therein ) augmented by a quasi-perturbative estimate for triple excitations (Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479). Extensive applications have shown that this method consistently yields results very close to those obtained by full configuration interaction (cf.: Lee, T. J.; Scuseria, G. E. In Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy; Langhoff, S. R., Ed.; Kluwer: Dordrecht, 1995). Note also, that at this level, the choice of a reference SCF wave fuction (UHF or ROHF) makes no significant difference to the final results (cf. e.g.: Stanton, J. F. J. Chem. Phys. 1994, 191, 371).
47. Coupled cluster calculation accounting for single and double excitations (see, e.g.: Bartlett, R. J. J. Phys. Chem. 1989, 93, 1697 and references therein ) augmented by a quasi-perturbative estimate for triple excitations (Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479). Extensive applications have shown that this method consistently yields results very close to those obtained by full configuration interaction (cf.: Lee, T. J.; Scuseria, G. E. In Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy; Langhoff, S. R., Ed.; Kluwer: Dordrecht, 1995). Note also, that at this level, the choice of a reference SCF wave fuction (UHF or ROHF) makes no significant difference to the final results (cf. e.g.: Stanton, J. F. J. Chem. Phys. 1994, 191, 371).
48. Coupled cluster calculation accounting for single and double excitations (see, e.g.: Bartlett, R. J. J. Phys. Chem. 1989, 93, 1697 and references therein ) augmented by a quasi-perturbative estimate for triple excitations (Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479). Extensive applications have shown that this method consistently yields results very close to those obtained by full configuration interaction (cf.: Lee, T. J.; Scuseria, G. E. In Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy; Langhoff, S. R., Ed.; Kluwer: Dordrecht, 1995). Note also, that at this level, the choice of a reference SCF wave fuction (UHF or ROHF) makes no significant difference to the final results (cf. e.g.: Stanton, J. F. J. Chem. Phys. 1994, 191, 371).
49. Dunning, T. H. J. Chem. Phys. 1989, 90, 1007.
50. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; DeFrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, M. C.; Pople, J. A. Gaussian, Inc.: Pittsburgh PA 1995.
51. ·+ is very difficult, we decided to use the structure of neutral TH for TH0.
52. 2d curves does not correspond to a common geometry of both states which is attained only in TH0, the conical intersection.
53. Bally, T.; Truttman, L.; Dai, S.; Williams, F. J. Am. Chem. Soc. 1995, 117, 7916.
54. IRC = intrinsic reaction coordinate (see: Gonzales, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154; J. Phys. Chem. 1990, 94, 5523).
55. IRC = intrinsic reaction coordinate (see: Gonzales, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154; J. Phys. Chem. 1990, 94, 5523).