Kinetic energy release distribution; H-loss from Benzene cation; Maximum entropy method; OTST theory; SACM model; C6H6+
Abstract :
[en] The kinetic energy release distributions (KERDs) associated with the hydrogen loss from the benzene cation and the deuterium loss from the perdeuteriobenzene cation have been remeasured on the metastable time scale and analyzed by the maximum entropy method. The experimental kinetic energy releases are larger than expected statistically, in contradistinction to what has been observed for the C-X fragmentations of the halogenobenzene cations. H(D) loss from C6H6+ (C6D6+) occurs via a conical intersection connecting the (2)A(2) and (2)A(1) electronic states. Two models are proposed to account for the experimental data: (i) a modified orbiting transition state theory (OTST) approach incorporating electronic nonadiabaticity; (ii) an electronically nonadiabatic version of the statistical adiabatic channel model ( SACM) of Quack and Troe. The latter approach is found to be preferable. It leads to the conclusion that the larger the energy stored in the transitional modes, which partly convert to the relative interfragment motion, the shorter the value of the reaction coordinate at which the adiabatic channels cross, and the larger the probability of undergoing the (2)A(2) -> (2)A(1) transition required for hydrogen loss.
Research center :
Laboratoire de Dynamique Moléculaire
Disciplines :
Chemistry
Author, co-author :
Gridelet, E.
Lorquet, Andrée ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Locht, Robert ; Université de Liège - ULiège > Département de Chimie (Faculté des Sciences) > Laboratoire de Dynamique Moléculaire (Sciences)
Lorquet, Jean-Claude ; Université de Liège - ULiège > Département de Chimie (Faculté des sciences) > Laboratoire de Dynamique Moléculaire (Sciences)
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Language :
English
Title :
Hydrogen atom loss from the benzene cation. Why is the kinetic energy release so large?
Alternative titles :
[fr] Perte d'un atome d'hydrogène par le cation du benzène. Pourquoi l'énergie cinétique libérée est-elle si importante?
Andlauer, B.; Ottinger, C. J. Chem. Phys. 1971, 55, 1471.
Rosenstock, H. M.; Larkins, J. T.; Walker, J. A. Int. J. Mass Spectrom. Ion Phys. 1973, 11, 309.
Chupka, W. A. In Chemical Spectroscopy and Photochemistry in the Vacuum-Ultraviolet; Sandorfy, C., Ausloos, P. J., Robin, M. B., Eds.; Reidel: Dordrecht, The Netherlands, 1974.
Eland, J. H. D.; Schulte, H. J. Chem. Phys. 1975, 62, 3835.
Eland, J. H. D.; Frey, R.; Schulte, H.; Brehm, B. Int. J. Mass Spectrom. Ion Phys. 1976, 21, 209.
Rosenstoek, H. M.; McCulloh, K. E.; Lossing, F. P. Int. J. Mass Spectrom. Ion Phys. 1977, 25, 327.
Baer, T.; Willett, G. D.; Smith, D.; Phillips, J. S. J. Chem. Phys. 1979, 70, 4076.
Jarrold, M. F.; Wagner-Redeker, W.; Illies, A. J.; Kirchner, N. J.; Bowers, M. T. Int. J. Mass Spectrom. Ion Processes 1984, 58, 63.
Kühlewind, H.; Neusser, H. J.; Schlag, E. W. J. Phys. Chem. 1984, 88, 6104.
Neusser, H. J.; Kühlewind, H.; Boesl, U.; Schlag, E. W. Ber. Bunsen Ges. Phys. Chem. 1985, 89, 276.
Kühlewind, H.; Kiermeier, A.; Neusser, H. J. J. Chem. Phys. 1986, 85, 4427.
kühlewind, H.; Kiermeier, A.; Neusser, H. J.; Schlag, E. W. J. Chem. Phys. 1987, 87, 6488.
Kiermeier, A.; Kühlewind, H.; Neusser, H. J.; Schlag, E. W.; Lin, S. H. J. Chem. Phys. 1988, 88, 6182.
Neusser, H. J. J. Phys. Chem. 1989, 93, 3897.
Grebner, T. L.; Neusser, H. J. Int. J. Mass Spectrom. 1999, 185/186/187, 517.
Klippenstein, S. J.; Faulk, J. D.; Dunbar, R. C. J. Chem. Phys. 1993, 98, 243.
Holland, D. M. P.; Shaw, D. A.; Sumner, I.; Bowler, M. A.; Mackie, R. A. ; Shpinkova, L. G.; Cooper, L.; Rennie, E. E.; Parker, J. E.; Johnson, C. A. F. Int. J. Mass Spectrom. 2002, 220, 31.
Klots, C. E. J. Chem. Phys. 1990, 93, 2513.
Klots, C. E. J. Chem. Phys. 1990, 93, 6585.
Klippenstein, S. J. Int. J. Mass Spectrom. Ion Processes 1997, 167/168, 235.
Klots, C. E. J. Chem. Phys. 1976, 64, 4269.
Bertrand, M.; Beynon, J. H.; Cooks, R. G. Int. J. Mass Spectrom. Ion Phys. 1972, 9, 346.
Jones, E. G.; Bauman, L. E.; Beynon, J. H.; Cooks, R. G. Org. Mass Spectrom. 1973, 7, 185.
Cooks, R. G.; Kim, K. C.; Keough, T.; Beynon, J. H. Int. J. Mass Spectrom. Ion Phys. 1974, 15, 271.
Migahed, M. D.; Abd El-Kader, F. H. Int. J. Mass Spectrom. Ion Phys. 1978, 28, 225.
Lifshitz, C. Int. J. Mass Spectrom. Ion Processes 1992, 118-119, 315.
Park, J.; Bersohn, R.; Oref, I. J. Chem. Phys. 1990, 93, 5700.
Chesnavich, W. J.; Bass, L.; Su, T.; Bowers, M. T. J. Chem. Phys. 1981, 74, 2228.
Blank, D. A.; Suits, A. G.; Lee, Y. T.; North, S. W.; Hall, G. E. J. Chem. Phys. 1998, 108, 5784.
Fati, D.; Lorquet, A. J.; Locht, R.; Lorquet, J. C.; Leyh, B. J. Phys. Chem. A 2004, 108, 9777.
Gridelet, E.; Lorquet, J. C.; Leyh, B. J. Chem. Phys. 2005, 122, 094106.
Chesnavich, W. J.; Bowers, M. T. J. Chem. Phys. 1977, 66, 2306.
Chesnavich, W. J.; Bowers, M. T. J. Am. Chem. Soc. 1977, 99, 1705.
Chesnavich, W. J.; Bowers, M. T. Prog. React. Kinet. 1982, 11, 137.
Baer, T.; Hase, W. L. Unimolecular Reaction Dynamics. Theory and Experiments; Oxford University: New York, 1996.
Laskin, J.; Lifshitz, C. J. Mass Spectrom. 2001, 36, 459.
Leyh, B.; Lorquet, J. C. Kinetic energy release distributions in mass spectrometry. In The Encyclopedia of Mass Spectrometry; Armentrout, P. B., Ed.; Elsevier: Amsterdam, 2003; Vol. 1; p 17.
Nicolaides, A.; Smith, D. M.; Jensen, F.; Radom, L. J. Am. Chem. Soc. 1997, 119, 8083.
Harvey, J. N.; Aschi, M.; Schwarz, H.; Koch, W. Theor. Chem. Acc. 1998, 99, 95.
Levine, R. D.; Kinsey, J. L. In Atom-Molecule Collision Theory. A Guide for the Experimentalist; Bernstein, R. B., Ed.; Plenum: New York, 1979.
Levine, R. D. Adv. Chem. Phys. 1981, 47, 239.
Levine, R. D.; Bernstein, R. B. In Dynamics of Molecular Collisions, Part B; Miller, W. H., Ed.; Plenum: New York, 1976.
Urbain, P.; Remade, F.; Leyh, B.; Lorquet, J. C. J. Phys. Chem. 1996, 100, 8003.
Urbain, P.; Leyh, B.; Remade, F.; Lorquet, A. J.; Flammang, R.; Lorquet, J. C. J. Chem. Phys. 1999, 110, 2911.
Quack, M.; Troe, J. Ber. Bunsen Ges. Phys. Chem. 1974, 78, 240.
Quack, M.; Troe, J. Ber. Bunsen Ges. Phys. Chem. 1975, 79, 469.
Lorquet, J. C.; Leyh, B. Statistical theories in mass spectrometry. In The Encyclopedia of Mass Spectrometry; Armentrout, P. B., Ed.; Elsevier: Amsterdam, 2003; Vol. 1; p 8.
Barber, M.; Elliot, R. M. 12th Annual Conference on Mass Spectrometry, Montreal, Canada, ASTM E-14, 1964.
Jennings, K. R. J. Chem. Phys. 1965, 43, 4176.
Barber, M.; Green, B. N.; Wolstenholme, W. A.; Jennings, K. R. Adv. Mass Spectrom. 1968, 4, 89.
Beynon, J. H.; Fontaine, A. E.; Lester, G. R. Int. J. Mass Spectrom. Ion Phys. 1972, 5, 341.
Cooks, R. G.; Beynon, J. H.; Caprioli, R. M.; Lester, G. R. Metastable Ions; Elsevier: Amsterdam, 1973.
Holmes, J. L.; Osborne, A. D. Int. J. Mass Spectrom. Ion Phys. 1977, 23, 189.
Szilagyi, Z.; Vekey, K. Eur. Mass Spectrom. 1995, 1, 507.
Rumpf, B. A.; Derrick, P. J. Int. J. Mass Spectrom. Ion Processes 1988, 82, 239.
Yeh, I. C.; Kim, M. S. Rapid Commun. Mass Spectrom. 1992, 6, 115.
Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas-Phase Ion and Neutral Thermochemistry, J. Phys. Chem. Ref. Data 1988, 17.
Levine, R. D.; Bernstein, R. B. Molecular Reaction Dynamics and Chemical Reactivity; Oxford University: New York, 1987.
Levine, R. D. Molecular Reaction Dynamics; Cambridge University Press: Cambridge, U.K., 2005.
Alhassid, Y.; Levine, R. D. J. Chem. Phys. 1977, 67, 4321.
Urbain, P.; Leyh, B.; Remade, F.; Lorquet, J. C. Int. J. Mass Spectrom. 1999, 185/186/187, 155.
Hoxha, A.; Locht, R.; Lorquet, A. J.; Lorquet, J. C.; Leyh, B. J. Chem. Phys. 1999, 111, 9259.
Gridelet, E.; Locht, R.; Lorquet, A. J.; Lorquet, J. C.; Leyh, B. Int. J. Mass Spectrom. 2003, 228, 389.
Gridelet, E.; Dehareng, D.; Locht, R.; Lorquet, A. J.; Lorquet, J. C.; Leyh, B. J. Phys. Chem. A 2005, 109, 8225.
Iachello, F.; Levine, R. D. Europhysics Lett. 1987, 4, 389.
Moon, J. H.; Choe, J. C.; Kim, M. S. J. Phys. Chem. A 2000, 104, 458.
Locht, R. Int. J. Mass Spectrom. Ion Processes 1995, 148, L17.
Servais, C.; Locht, R. Chem. Phys. Lett. 1995, 236, 96.
Zamir, E.; Levine, R. D. Chem. Phys. 1980, 52, 253.
Delos, J. B. J. Chem. Phys. 1973, 59, 2365.
Bandrauk, A. D.; Laplante, J. P. J. Chem. Phys. 1976, 65, 2592.
Desouter-Lecomte, M.; Lorquet, J. C. J. Chem. Phys. 1979, 71, 4391.
Nikitin, E. E.. Theory of Elementary Atomic and Molecular Processes in Gases; Clarendon Press: Oxford, U.K., 1974.
Desouter-Lecomte, M.; Dehareng, D.; Leyh-Nihant, B.; Praet, M. T.; Lorquet, A. J.; Lorquet, J. C. J. Phys. Chem. 1985, 89, 214.
Desouter-Lecomte, M.; Leyh-Nihant, B.; Praet, M. T.; Lorquet, J. C. J. Chem. Phys. 1987, 86, 7025.
Leyh-Nihant, B.; Lorquet, J. C. J. Chem. Phys. 1988, 88, 5606.
Lorquet, J. C.; Leyh, B. Nonadiabatic Reactions. In The Encyclopedia of Mass Spectrometry; Armentrout, P. B., Ed.; Elsevier: Amsterdam, 2003; Vol. 1; p 33.
Mardis, K. L.; Sibert, E. L., III. J. Chem. Phys. 1998, 109, 8897.
