Femtochemistry of norrish type-1 reactions: I. Experimental and theoretical studies of acetone and related ketones on the s1 surface

ChemPhysChem

Volumn 2, Issue 5, 2001, Pages 273-293

  Diau, Eric W G ^a   Kötting, Garsten ^a   Zewail, Ahmed H ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Acetone; Conical intersection; Femtochemistry; Mass spectrometry; Norrish reactions

Indexed keywords

BOND STRENGTH (CHEMICAL); CARBON; DENSITY FUNCTIONAL THEORY; DISSOCIATION; DYNAMICS; ENERGY BARRIERS; MASS SPECTROMETRY; POTENTIAL ENERGY; QUANTUM CHEMISTRY;

CONICAL INTERSECTION; DISSOCIATION DYNAMICS; FEMTOCHEMISTRY; FEMTOSECOND PUMP PROBES; INTER-SYSTEM CROSSINGS; NANOSECOND TIME SCALE; NORRISH REACTION; THEORETICAL CALCULATIONS;

ACETONE;

EID: 23044526322     PISSN: 14394235     EISSN: None     Source Type: Journal    
DOI: 10.1002/1439-7641(20010518)2:5<273::aid-cphc273>3.0.co;2-h     Document Type: Article

References (84)

1. W. A. Noyés, in Photochemistry and Reaction Kinetics (Eds.: P. G. Ashmore. F. S. Dainton, T. M. Sugden), Cambridge University Press, Cambridge, 1967, pp. 1 -25.
2. J. Michl, V. Bonaic-Koutecky, Electronic Aspects of Organic Photochemistry, Wiley, New York, NY, 1990.
3. N. J. Turro, Modern Molecular Photochemistry, University Science Books, Sausalito, CA, 1991.
4. J. Kopecky, Organic Photochemistry: AVisual Approach, VCH, New York, NY, 1992.
5. M. Kiessinger, J. Michl, Excited States and Photochemistry of Organic Molecules, VCH, New York, NY, 1995.
6. L Salem, J. Am. Chem. Soc. 1974, 96, 3486-3501, and references therein.
7. M. Reinsch, M. Kiessinger, J. Phys. Org. Chem. 1990, 3, 81 -88.
8. a)O. Setokuchi, Y. Simizu, J. Mol. Struct. (Theochem) 1997, 401, 29-33
9. b) O. Setokuchi, S. Matuzawa, Y. Shimizu, Chem. Phys. Lett. 1998,284,19-23.
10. H. Sakurai, S. Kalo, J. Mol. Struct. (Theochem) 1999, 461, 145-152.
11. X. Li, Z. Li, S. Ma, Sei. China Ser. B 1999, 42, 373-381.
12. D. Liu, W. Fang, X. Fu, Chem. Phys. Lett. 2000, 325, 86-92.
13. E. K. C. Lee, R. S. Lewis, Adv. Photochem. 1980, 12, 1 - 95, and references therein.
14. R. A. Copeland, D.R. Crosley, Chem. Phys. Lett. 1985, 115, 362-368.
15. a) D. J. Donaldson, S. R. Leone, J. Chem. Phys. 1986, 85, 817-824
16. b) E. L. Woodbridge,T. R. Fletcher, S. R. Leone,/ Phys. Chem. 1988,92,5387-5393.
17. P.D. Lightfoot, S.P. Kirwan, M.J. Pilling, J. Phys. Chem. 1988, 92, 4938-4946.
18. K. A. Trentelman, S. H. Kable, D. B. Moss, P. L Houston, J. Chem. Phys. 1989, 91,7498-7513.
19. Y. Haas, Spectrochim. Acta Part A 1990, 46, 541-549, and references therein.
20. G. E. Hall, V. Bout, T. J. Sears, J. Chem. Phys. 1991, 94,4182-4188.
21. LD. Waits, R.J. Horwitz, J.A. Guest, Chem. Phys. 1991, 155, 149-156.
22. S. W. North, D. A. Blank, J. D. Gezelter, C. A. Longfellow, Y.T. Lee, J. Chem. Phys. 1995, 102,4447-4460.
23. S.K. Kim, S. Pedersen, A.H. Zewail, J. Chem. Phys. 1995, 103, 477-480.
24. T. Shibata, T. Suzuki, Chem. Phys. Lett. 1996, 262, 115 -119.
25. C. Maul, K. Gericke, Int. Rev. Phys. Chem. 1997, 16, 1 -79, and references regarding the three-body photodissociation topics therein.
26. a) S.A. Buzza, E.M. Snyder, A.W. Castleman.Jr., J. Chem. Phys. 1996, 104, 5040-5047
27. b)S.A. Buzza, E.M. Snyder, D.A. Card, D.E. Folmer, A.W. Castleman, Jr., J. Chem. Phys. 1996,105,7425-7431
28. Q.Zhong, L Poth, A.W. Castleman, Jr., J. Chem. Phys. 1999, 110,192-196.
29. C. Majumder, 0. D. Jayakumar, R. K. Vatsa, S. K. Kulshreshtha, J. P. Mittal, Chem. Phys. Lett. 1999, 304, 51 -59.
30. a) J.C. Owrutsky, A.P. Baronavski, J. Chem. Phys. 1998, IDS, 6652-6659
31. b) J. C. Owrutsky, A. P. Baronavski, J. Chem. Phys. 1999,110,11 206 -11213.
32. P. Farmanara, V. Stert, W. Radloff, Chem. Phys. Lett. 2000, 320, 697-702.
33. M. Emrich, P. Warneck, J. Phys. Chem. A 2000, 104, 9436-9442.
34. D. A. Hansen, E. K. C. Lee, J. Chem. Phys. 1975, 62, 183-189.
35. P. R. Bunker, P. Jensen, Mo/ecu/ar Symmetry and Spectroscopy, 2nd ed., NRC Research Press, Ottawa, ON, 1998, pp.435-439.
36. D.W. Liao, A. M. Mebel, M. Hayashi, Y.J. Shiu, Y.T. Chen, S. H. Lin, J. Chem. Phys. 1999, 111,205-215.
37. a) M. Baba, I. Hanazaki, Chem. Phys. Lett. 1983, 103, 93-97;
38. b) M. Baba, 1. Hanazaki, U. Nagashima, J. Chem. Phys. 1985, 82, 3938-3947.
39. G. M. Breuer, E. K. C. Lee, J. Phys. Chem. 1971, 75, 989 - 990.
40. a)O.Anner,H.Zuckermann, Y.Haas, J.Phys. Chem. 1985,89,1336-1339;
41. b) H. Zuckermann, B. Schmits, Y. Haas, J. Phys. Chem. 1988, 92, 4835-4837
42. H. Zuckermann, B. Schmits, Y. Haas, Chem. Phys. Lett. 1988, 151, 323-327
43. H. Zuckermann, B. Schmits, Y. Haas, J. Phys. Chem. 1989, 93, 4083-4091.
44. J. Heicklen, J. Am. Chem. Soc. 1959, 81, 3863-3866.
45. G. Hancock, K.R. Wilson, in Proc. Fourth Int. Symp. Molecular Beams (Cannes, France) 1973, pp.511 -533.
46. N. J. Turro, W. E. Farenth, A. Devaquet, J. Am. Chem. Soc. 1976, 98, 7425-7427.
47. E. W.-G. Diau, C. Kötting, A. H. Zewail, ChemPhysChem. 2001,2, 294-309, the following paper in this issue.
48. [29,33]
49. -1∼1.2] and it is not obviously seen in the plot (Figure 4 A) due to the limitation of the pumpprobe delay times of the transients.
50. ptotx, = 615 nm) in our experiments, it is expected to establish the resonance-enhanced condition for the MPI signal of a cold acetyl radical at the CCO bending angle slightly larger than the angle at the equilibrium geometry (see also Figure 23).
51. J. D. Goddard, G. Orlova, 1. Chem. Phys. 1999, 111. 7705 - 7712.
52. M. Merchan, B. O. Roos, R. McDiardmid, X. Xing, J. Chem. Phys. 1996, 104. 1791-1804.
53. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.
54. C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 1988,37, 785.
55. W. Hehre, L. Radom, P. von R. Schleyer, J.A. Pople, Ab Initia Molecular Orbital Theory, Wiley, New York, NY, 1986.
56. F. Jensen, Introduction to Computational Quantum Chemistry, Wiley, New York, NY, 1998.
57. K. B. Wiberg, R. E. Stratmann, M J. Frisch, Chem. Phys. Lett. 1998,297,60-64.
58. D.J. Tozer, N.C. Handy, Phys. Chem. Chem. Phys. 2000, 2, 2117-2121.
59. a) P. Brim, L. OToole, S. Couris, D. Jardine, J. Chem. Soc. faraday Trans. 1991, 87, 2891-2895
60. b) L OToole, P. Brim, C. Kosmidis, G. Boulakis, P. Tsekeris, J. Chem. Soc. Faraday Trans. 1991, 87, 3343-3351.
61. Gaussion 98 (Rev.A.9), M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, O.K. Malick, A.D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L Martin, D.J. Fox, T. Keith, M. A. AI-Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill, B.G. Johnson, W. Chen, M.W. Wong, J.L Andres, M. Head-Gordon, E.S. Replogle, J.A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998.
62. See, for example, E.W.-G. Diau, S.C. Smith, J. Phys. Chem. 1996, 100, 12349-12354.
63. T. Baer, W. L. Hase, Unimolecular Reaction Dynamics, Oxford University Press, New York, NY, 1996.
64. The local minimum was found located at RC=4.240 and 3.784 A based on the CASSCF and the DFT calculations, respectively. The spurious point (local minimum) located in the middle of the MEP may be due to the following reason: The long-range dipole-dipole interaction becomes predominant over the short-range CC valence-bond interaction at longer separations leading to a van der Waals complex as an intermediate along the RC. Therefore, at RC 4 A, the single a-CC bond-breaking MEP is characterized mainly by the stronger long-range interaction between the hydrogen atom of the departing methyl group and the radical center of the acetyl group. This feature is best demonstrated by the drastic change of the geometry along the MEP near the local minimum region, where the departing methyl group suddenly flips to have a nearly linear CMC configuration. This is also the reason why the 0 angle predicted at the UB3LYP/6-31G(d) level suffered a dramatic variation in the RC range between 3.8 and 4.2 A, as shown in Figure 9 A.
65. a) N. N. Yakovlev, I. V. Dyumaeva, I. A. Godunov, RUSS. J. Phys. Chem. 1992, 66, 367-371;
66. b) N. N. Yakovlev, I.A. Godunov, fiuss. J. Phys. Chem. 1995, 69.507-510.
67. l. N. Ragazos, M. A. Robb, F. Bernard!, M. Olivucci, Chem. Phys. Lett. 1992, 797,217-223.
68. W. Domcke, G. Stock, Adv. Chem. Phys. 1997, 100, 1.
69. D. R. Yarkony, Ace. Chem. Res. 1998, 31, 511-518.
70. M. Kiessinger, Angew. Chem. 1995, 107, 597-599;
71. Angew. Chem. Int. Ed. fngf.1995, 34, 549-551.
72. F. Bernard!, M. Olivucci, M. A. Robb, Chem. Soc. Rev. 1996, 25, 321 -328, and references therein.
73. S. Wilsey, K.N. Houk, A.H. Zewail, J. Am. Chem. Soc. 1999, 121, 5772-5786, and references therein.
74. a) E. W.-G. Diau, O. K. Abou-Zied, A. A. Scala, A. H. Zewail, J. Am. Chem. Soc. 1998, 120, 3245 - 3246
75. b) E. W.-G. Diau, S. De Feyter, A. H. Zewail, Chem. Phys. Lett. 1999,304,134-144
76. S. De Feyter, E. W.-G. Diau, A. H. Zewail, phys. Chem. Chem. Phys. 2000, 2, 877-883.
77. G. Herzberg, Molecular Spectra and Molecular Structure, III. Electronic Spectra and Electronic Structures of Polyatomic Molecules, Van Nostrand, New York, NY, 1966.
78. A. Loettgers, A. Untch, H. Keller, R. Schinke, H. Werner, C. Bauer, P. Rosmus, J. Chem. Phys. 1997, 106, 3186-3204, and references therein.
79. [38]
80. G. S. Hammond, J. Am. Chem. Soc. 1955, 77, 334-338.
81. N. C. Yang, E. D. Feit, M. H. Hui, N. J. Turro, J. C. Dalton, J. Am. Chem. Soc. 1970,92,6974-6976.
82. A. H. Zewail, Femtochemistry: Ultrafast Dynamics of the Chemical Bond, Vol. l and II, World Scientific, Singapore, 1994, and references therein.
83. E. W.-G. Diau, S. De Feyter, A. H. Zewail, J. Chem. Phys. 1999, 110, 9785-9788.
84. D. Zhong, E W.-G. Diau, T. M. Bernhardt, S. De Feyter, J. D. Roberts, A. H. Zewail, Chem. Phys. Lett. 1998, 298, 129-140.