Relaxation paths from a conical intersection: The mechanism of product formation in the cyclohexadiene/hexatriene photochemical interconversion

Journal of Physical Chemistry A

Volumn 101, Issue 11, 1997, Pages 2023-2032

  Garavelli, Marco ^a   Celani, Paolo ^b   Fato, Monica ^a   Bearpark, Michael J ^b   Smith, Barry R ^b   Olivucci, Massimo ^a   Robb, Michael A ^b  

^a UNIVERSITY OF BOLOGNA   (Italy)

^b KING'S COLLEGE LONDON   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALGORITHMS; CHEMICAL RELAXATION; COMPUTATIONAL METHODS; MATHEMATICAL MODELS; MOLECULAR DYNAMICS; REACTION KINETICS;

CYCLOHEXADIENE (CHD) PHOTOLYSIS; HEXATRIENE (HT) PHOTOLYSIS; INITIAL RELAXATION DIRECTIONS (IRD); PHOTOPRODUCT FORMATION;

PHOTOLYSIS;

EID: 0031099001     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp961554k     Document Type: Article

References (46)

1. Klessinger, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 549-551.
2. Michl, J.; Bonacic-Koutecky, V. Electronic Aspects of Organic Photochemistry; Wiley: New York, 1990.
3. For recent results see: (a) Celani, P.; Bernardi, F.; Olivucci, M.; Robb, M. A. J. Chem. Phys. 1995, 102, 5733.
4. (b) Heumann, B.; Schinke, R. J. Chem. Phys. 1994, 101, 7488-7499.
5. (c) Yarkony, D. R. J. Chem. Phys. 1994, 100, 3639.
6. (d) Mielke, S. L.; Tawa, G. J.; Truhlar, D. G.; Schwenke D. W. J. Am. Chem. Soc. 1993, 115, 6436.
7. (e) Muller, H. et al. Chem. Phys. Lett. 1992, 197, 599.
8. (f) Woywod, C.; Domcke, W.; Sobolewski, A. L.; Werner H-J. J. Chem. Phys. 1994, 100, 1400.
9. (g) Atchity, G. J.; Xantheas, S. S.; Elbert, S. T.; Ruedenberg, K. J. Chem. Phys. 1991, 94, 8054.
10. (a) Petek, H.; Bell, A. J.; Christensen, R. L.; Yoshiara, K. SPIE, 1992, 1638, 345-356.
11. (b) Petek, H.; Bell, A. J.; Choi, Y. S.; Yoshiara, K.; Tounge, B. A.; Christensen, R. L. J. Chem. Phys. 1993, 98, 3777-3794.
12. Celani, P.; Garavelli, M.; Ottani, S.; Bernardi, F.; Robb, M. A.; Olivucci, M. J. Am. Chem. Soc. 1995, 117, 11584-11585.
13. -1, the decay probability is vanishing small. However, as we approach a point where the surfaces cross, the decay probability becomes unity.
14. (a) Rejto, P. A.; Bindewald, E.; Chandler, D. Nature 1995, 375, 129-131.
15. (b) Liu, Q.; Wang, J.-K.; Zewail, A. H. J. Phys. Chem. 1995, 99, 11321.
16. (a) Jimenez, R.; Fleming, G. R.; Kumar, P. V.; Maroncelli, M. Nature 1994, 369, 471-473.
17. (b) Liu, Q.; Wang, J.-K.; Zewail, A. H. J. Phys. Chem. 1995, 99, 11309.
18. (c) Heikal, A. A.; Chong, S. H.; Baskin, J. S.; Zewail, A. H. Chem. Phys. Lett. 1995, 242, 380-389.
19. (d) Zhong, Q.; Wang, Z.; Sun, Y.; Zhu, Q.; Kong, F. Chem. Phys. Lett. 1996, 248, 277-282.
20. 1 lifetime of ∼1 ps.
21. 1 lifetime of ∼1 ps.
22. (a) Koppel, H.; Domcke, W.; Cederbaum, L. S. Adv. Chem. Phys. 1984, 57, 59.
23. (b) Manthe, U.; Koppel, H. J. Chem. Phys, 1990, 93, 1658.
24. Truhlar, D. G.; Steckler, R.; Gordon, M. S. Chem. Rev. 1987, 87, 217. Truhlar, D. G.; Gordon M. S. Science 1990, 249, 491.
25. Truhlar, D. G.; Steckler, R.; Gordon, M. S. Chem. Rev. 1987, 87, 217. Truhlar, D. G.; Gordon M. S. Science 1990, 249, 491.
26. McKee, M. L.; Page M. in Reviews in Computational Chemistry; Lipkowiz, K. B., Boyd, D. B., Eds.; VCH: New York, 1993; 4, pp 35-65.
27. Celani, P.; Ottani, S.; Olivucci, M.; Bernardi, F.; Robb, M. A. J. Am. Chem. Soc. 1994, 116, 10141-10151.
28. Heller, H. G.; Elliot, C. C.; Koh, K.; Al-Shihry, S.; Whittall, J. In Photochemistry and Polymeric Systems; Eds. Kelly, J. M., Mc Ardle, C. B., de F. Maunder, M. J., Eds.; The Royal Society of Chemistry: London, 1993; pp 156-168.
29. (a) Jacobs, H. J. C.; Havinga, E. Photochemistry of Vitamin D and Its Isomers and of Simple Trienes. In Advances in Photochemistry; Pitts, J. N., Jr.; Hammond, G. S.; Gollnick, K. Eds; John Wiley & Sons: New York, 1979; Vol. 11, pp 305-373.
30. (b) Dauben, W. G.; McInnis, E. L.; Mincho, D. M.; Photochemical Rearrangements in Trienes. In Rearrangements in Ground and Exited States; De Mayo, P., Ed.; Academic Press: London, 1980; Vol. 3, pp 91-129.
31. (a) Jacobs, H. J. C. Pure Appl. Chem. 1995, 67, 63-70.
32. (b) Brouwer, A. M.; Cornelisse, J. and Jacobs, H. J. C. J. Photochem. Photobiol A: Chem. 1988, 42, 117.
33. (c) Brouwer, A. M.; Cornelisse, J.; Jacobs, H. J. C. J. Photochem. Photobiol., A. 1988, 42, 313.
34. Atchity, G. J.; Xantheas, S. S.; Ruedenberg, K. J. Chem. Phys., 1991, 95, 1862-1876.
35. Gonzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523-5527.
36. Celani, P.; Robb, M. A.; Garavelli, M.; Bernardi, F.; Olivucci, M. Chem. Phys. Lett. 1995, 243, 1-8.
37. Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian 92, Revision B; Gaussian, Inc.: Pittsburgh, PA, 1992.
38. Roos, B. O. Adv. Chem. Phys. 1987, 69, 399-446.
39. Andersson, K.; Malmqvist, P.-A.; Ross, B. O. J. Chem. Phys. 1992, 96, 1218. The CAS-PT2F method is implemented in MOLCAS, Version 2. Andersson, K.; Blomberg, M. R. A.; Fülscher, M.; Kellö, V.; Lindh, R.; Malmqvist, P.-A.; Noga, J.; Olsen, J.; Roos, B. O.; Sadlej, A. J.; Siegbahn, P. E. M.; Urban, M.; Widmark, P. O. MOLCAS, Version 2; University of Lund: Lund, Sweden, 1991.
40. Andersson, K.; Malmqvist, P.-A.; Ross, B. O. J. Chem. Phys. 1992, 96, 1218. The CAS-PT2F method is implemented in MOLCAS, Version 2. Andersson, K.; Blomberg, M. R. A.; Fülscher, M.; Kellö, V.; Lindh, R.; Malmqvist, P.-A.; Noga, J.; Olsen, J.; Roos, B. O.; Sadlej, A. J.; Siegbahn, P. E. M.; Urban, M.; Widmark, P. O. MOLCAS, Version 2; University of Lund: Lund, Sweden, 1991.
41. (a) McDouall, J. J. W.; Peasley, K.; Robb, M. A. Chem. Phys. Lett. 1988, 148, 183.
42. (b) Bernardi, F.; Bottoni, A.; Celani, P.; Olivucci, M.; Robb, M. A.; Venturini, A. Chem. Phys. Lett. 1992, 192, 229-235.
43. Smith, B. R.; Bearpark, M. J.; Robb, M. A.; Bernardi, F.; Olivucci, M. Chem. Phys. Lett. 1995, 242, 27-32.
44. ○, can be expected to access the ground state in the region near "α + 180"○ (see Figure 10b). For instance, the small number of trajectories entering the MCPD channel start near 126°, while the MEP leading to MCPD was found at an angle of 306° (i.e. ∼126 + 180). Although, of course, the trajectories are moving in all degrees of freedom, this simple interpretation in terms of angles in the branching space seems successful (presumably because most of the initial motion is in the branching space). Similarly, large yields of CHD correspond to finding MEP to CHD on the "opposite" side of the circle. Due to the very small projection of the MCPD channel into the branching space (see subsection (ii)), trajectories decaying near the apex of the cone are unlikely to populate this channel.
45. (a) Matuszewski, B.; Burgstahler, A. W.; Givens, R. S. J. Am. Chem. Soc. 1982, 104, 6875.
46. (b) Dauben, W. G.; Rabinowitz, J.; Vietmeyer, N. D.; Wendschuh, P. H. J. Am. Chem. Soc. 1972, 94, 4285.