Kinetic energy release; Metastable dissociation; Maximum entropy method; Energy partitioning; Phase space sampling
Abstract :
[en] The kinetic translational energy released in the unimolecular fragmentation reaction C6H5Br+->C6H5++Br has been experimentally studied in the microsecond time scale and theoretically analyzed by the maximum entropy formalism. The appropriate functional form relating the actual distribution to its prior distribution (eq.2.3) involves the square root of the kinetic energy (i.e. the momentum associated with the relative translational energy). A value of 0.26+/-0.02 eV is obtained by the entropy deficiency distribution at an internal energy of 0.85 eV above the reaction threshold. From this value, it can be concluded that 77% of the transition state phase space is efficiently sampled.
Research Center/Unit :
Laboratoire de Dynamique Moléculaire
Disciplines :
Chemistry
Author, co-author :
Urbain, P.
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Lorquet, Jean-Claude ; Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences)
Language :
English
Title :
Unimolecular Reaction Dynamics from Kinetic Energy Release Distributions. 2. A Study of the Reaction C6H5Br+->C6H5++Br by the Maximum Entropy Method.
Publication date :
1996
Journal title :
Journal of Physical Chemistry
ISSN :
0022-3654
eISSN :
1541-5740
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
100
Issue :
19
Pages :
8003-8007
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
FRFC - Fonds de la Recherche Fondamentale Collective
scite shows how a scientific paper has been cited by providing the context of the citation, a classification describing whether it supports, mentions, or contrasts the cited claim, and a label indicating in which section the citation was made.
Bibliography
Forst, W. Theory of Unimolecular Reactions; Academic Press: New York, 1973.
Marcus, R. A. Chem. Phys. Lett. 1988, 144, 208.
Klippenstein, S. J.; Marcus, R. A. J. Chem. Phys. 1989, 91, 2280.
Chesnavich, W. J.; Bowers, M. T. J. Am. Chem. Soc. 1977, 99, 1705.
Chesnavich, W. J.; Bass, L.; Su, T.; Bowers, M. T. J. Chem. Phys. 1981, 74, 2228.
Klots, C. E. J. Chem. Phys. 1976, 64, 4269.
Klots, C. E. Acc. Chem. Res. 1988, 21, 16.
Levine, R. D.; Bernstein, R. B. In Dynamics of Molecular Collisions, Part B; Miller, W. H., Ed.; Plenum: New York, 1976.
Levine, R. D.; Kinsey, J. L. In Atom-Molecule Collision Theory; Bernstein, R. B., Ed.; Plenum: New York, 1979.
Levine, R. D. Adv. Chem. Phys. 1981, 47, 239.
Levine, R. D.; Bernstein, R. B. Molecular Reaction Dynamics and Chemical Reactivity; Oxford University: New York, 1987.
Kaplan, H.; Levine, R. D. Chem. Phys. 1976, 18, 103.
Tamir, M.; Levine, R. D. Chem. Phys. 1976, 18, 125.
Pollak, E.; Levine, R. D. Chem. Phys. 1977, 21, 61.
Holmes, J. L.; Osborne, A. D. Int. J. Mass Spectrom. Ion Phys. 1977, 23, 189.
Holmes, J. L.; Terlouw, J. K. Org. Mass Spectrom. 1980, 15, 383.
Lifshitz, C. J. Phys. Chem. 1983, 87, 2304.
Levsen, K. Fundamental Aspects of Organic Mass Spectrometry; Verlag Chemie: Weinheim, 1978.
Illenberger, E.; Momigny, J. Gaseous Molecular Ions; Springer-Verlag: New York, 1992.
Cooks, R. G.; Beynon, J. H.; Caprioli, R. M.; Lester, G. R. Metastable Ions; Elsevier: Amsterdam, 1973.
Cho, Y. S.; Choe, J. C.; Kim, M. S. J. Phys. Chem. 1995, 99, 8645.
Momigny, J.; Locht, R.; Caprace, G. Int. J. Mass Spectrom. Ion Phys. 1986, 71, 159.
Momigny, J.; Locht, R. Chem. Phys. Lett. 1993, 211, 161.
Zamir, E.; Levine, R. D. Chem. Phys. 1980, 52, 253.
Malinovich, Y.; Arakawa, R.; Haase, G.; Lifshitz, C. J. Phys. Chem. 1985, 89, 2253.
Baer, T.; Tsai, B. P.; Smith, D.; Murray, P. T. J. Chem. Phys. 1976, 64, 2460.
Baer, T.; Kury, R. Chem. Phys. Lett. 1982, 92, 659.
Rosenstock, H. M.; Stockbauer, R.; Pair, A. C. J. Chem. Phys. 1980, 73, 773.
Pratt, S. T.; Chupka, W. A. Chem. Phys. 1981, 62, 153.
Brand, W. A.; Stocklöv, J.; Walther, H. J. Int. J. Mass Spectrom. Ion Processes 1984, 59, 1.
Burgers, P. C.; Holmes, J. L. Int. J. Mass Spectrom. Ion Processes 1984, 58, 15.
Ewing, G. E. J. Chem. Phys. 1979, 71, 3143.
Beswick, J. A.; Jortner, J. Adv. Chem. Phys. 1981, 47, 363.
Barber, M.; Elliot, R. M. Presented at the 12th Annual Conference on Mass Spectrometry and Allied Topics, Montreal, 1964.
Boyd, R. K.; Beynon, J. H. Org. Mass Spectrom. 1977, 12, 163.
Beynon, J. H.; Fontaine, A. E.; Lester, G. R. Int. J. Mass Spectrom. Ion Phys. 1972, 8, 341.
Kim, B. J.; Kim, M. S. Rapid Commun. Mass Spectrom. 1990, 4, 327.
Kim, Y. H.; Kim, M. S. Rapid Commun. Mass Spectrom. 1991, 5, 25.
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.
Yeh, I. C.; Kim, M. S. Rapid Commun. Mass Spectrom. 1992, 6, 293.
Beyer, T.; Swinehardt, D. F. Commun. ACM 1973, 16, 379.
Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
Levine, R. D. Ber. Bunsen-Ges. Phys. Chem. 1974, 78, 113.
Lorquet, J. C. Mass Spectrom. Rev. 1994, 13, 233.
Marcus, R. A. J. Chem. Phys. 1966, 45, 4500.
Miller, W. H.; Handy, N. C.; Adams, J. E. J. Chem. Phys. 1980, 72, 99.
This website uses cookies to improve user experience. Read more
Save & Close
Accept all
Decline all
Show detailsHide details
Cookie declaration
About cookies
Strictly necessary
Performance
Strictly necessary cookies allow core website functionality such as user login and account management. The website cannot be used properly without strictly necessary cookies.
This cookie is used by Cookie-Script.com service to remember visitor cookie consent preferences. It is necessary for Cookie-Script.com cookie banner to work properly.
Performance cookies are used to see how visitors use the website, eg. analytics cookies. Those cookies cannot be used to directly identify a certain visitor.
Used to store the attribution information, the referrer initially used to visit the website
Cookies are small text files that are placed on your computer by websites that you visit. Websites use cookies to help users navigate efficiently and perform certain functions. Cookies that are required for the website to operate properly are allowed to be set without your permission. All other cookies need to be approved before they can be set in the browser.
You can change your consent to cookie usage at any time on our Privacy Policy page.