Direct observation of disrotatory ring-opening in photoexcited cyclobutene using ab initio molecular dynamics [7]

Journal of the American Chemical Society

Volumn 122, Issue 26, 2000, Pages 6299-6300

  Ben Nun, M ^a   Martínez, Todd J ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL REACTION KINETICS; COMPUTER SIMULATION; LETTER; MOLECULAR DYNAMICS; ORGANIC CHEMISTRY; PREDICTION; RAMAN SPECTROMETRY; REACTION ANALYSIS;

EID: 0343953619     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9943896     Document Type: Letter

References (30)

1. Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Verlag Chemie: Weinheim/Deerfield Beach, 1970.
2. Zimmerman, H. E. Acc. Chem. Res. 1971, 4, 272.
3. Goddard, W. A., III. J. Am. Chem. Soc. 1970, 92, 7520-7521.
4. Analysis of the product stereochemistry using alkyl-substituted reactants cannot show that the reaction is concerted, which is a prerequisite for the applicability of the WH rules. Furthermore, the addition of substitutents could alter the reaction path. Finally, the short time scale of the resonance Raman experiment precludes drawing any conclusions beyond whether the initial motions follow the WH-predicted pathway.
5. Baldwin, J. E.; Krueger, S. M. J. Am. Chem. Soc. 1969, 91, 6444.
6. Dauben, W. G.; Rabinowitz, J.; Vietmeyer, N. D.; Wendschuh, P. H. J. Am. Chem. Soc. 1972, 94, 4285.
7. Spangler, C. W.; Hennis, R. P. Chem. Commun. 1972, 24.
8. Trulson, M. O.; Dollinger, G. D.; Mathies, R. A. J Am. Chem. Soc. 1987, 109, 586.
9. Trulson, M. O.; Dollinger, G. D.; Mathies, R. A. J. Chem. Phys. 1989, 90, 4274.
10. Leigh, W. J. Can. J. Chem. 1993, 71, 147.
11. Craig, N. C.; Borick, S. S.; Tucker, T.; Xia, Y.-Z. J. Phys. Chem. 1991, 95, 3549.
12. Wiberg, K. B.; Rosenberg, R. E. J. Phys. Chem. 1992, 96, 8282.
13. Lawless, M. K.; Wickham, S. D.; Mathies, R. A. J. Am. Chem. Soc. 1994, 116, 1593.
14. Lawless, M. K.; Wickham, S. D.; Mathies, R. A. Acc. Chem. Res. 1995, 28, 493.
15. Negri, F.; Orlandi, G.; Zerbetto, F.; Zgierski, M. Z. J. Chem. Phys. 1995, 103, 5911.
16. Lord, R. C.; Rea, D. G. J. Am. Chem. Soc. 1957, 79, 2401.
17. Ben-Nun, M.; Martínez, T. J. Chem. Phys. Lett. 1998, 298, 57.
18. Martínez, T. J. Chem. Phys. Lett. 1997, 272, 139.
19. Celani, P.; Bernardi, F.; Olivucci, M.; Robb, M. A. J. Chem. Phys. 1995, 102, 5733.
20. Rappe, A. K.; Goddard, W. A., III unpublished.
21. Bauschlicher, C. W.; Langhoff, S. R.; Taylor, P. R. Adv. Chem. Phys. 1990, 77, 103.
22. Adam, W.; Oppenlander, T.; Zang, G. J. Am. Chem. Soc. 1985, 107, 3921.
23. Hillery, M.; O'Connell, R. F.; Scully, M. O.; Wigner, E. P. Phys. Rep. 1984, 105, 121.
24. MOLPRO is a package of ab initio programs written by H.-J. Werner and P. J. Knowles, with contributions from R. D. Amos, A. Bernhardsson, A. Berning, P. Celani, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, C. Hampel, G. Hetzer, T. Korona, R. Lindh, A. W. Lloyd, S. J. McNicholas, F. R. Manby, W. Meyer, M. E. Mura, A. Nicklass, P. Palmieri, R. Pitzer, G. Rauhut, M. Schütz, H. Stoll, A. J. Stone, R. Tarroni, and T. Thorsteinsson.
25. Dunning, T. H., Jr. J. Chem. Phys. 1989, 90, 1007.
26. The orbitals were determined by state-averaging (with equal weight) over only the lowest three states in a CAS(4/4) wave function. This was followed by MRCI including single excitations. This more accurate wave function yields a vertical excitation energy of approximately 7.7 eV, compared to 8.6 eV for the wave function used in the AIMS simulations.
27. Jaguar, v3.5; Schrodinger, Inc.: Portland, OR, 1998.
28. Goddard, W. A., III; Dunning, T. H., Jr.; Hunt, W. J.; Hay, P. J. Acc. Chem. Res. 1973, 6, 368-376.
29. Zewail, A. H. J. Phys. Chem. 1996, 100, 12701.
30. Song, L.; El-Sayed, M. A. J. Am. Chem. Soc. 1998, 120, 8889.