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Titolo:
COLLISIONAL ENERGY-TRANSFER, INTRAMOLECULAR VIBRATIONAL-RELAXATION AND UNIMOLECULAR REACTIONS
Autore:
SMITH IWM;
Indirizzi:
UNIV BIRMINGHAM,SCH CHEM,POB 363 BIRMINGHAM B15 2TT W MIDLANDS ENGLAND
Titolo Testata:
Journal of the Chemical Society. Faraday transactions
fascicolo: 21, volume: 93, anno: 1997,
pagine: 3741 - 3750
SICI:
0956-5000(1997)93:21<3741:CEIVA>2.0.ZU;2-K
Fonte:
ISI
Lingua:
ENG
Soggetto:
INDUCED FLUORESCENCE MEASUREMENTS; DIPOLE-MOMENT FUNCTION; HIGH-PRESSURE RANGE; TEMPERATURE-DEPENDENCE; EMISSION-SPECTROSCOPY; INFRARED-EMISSION; LASER-ABSORPTION; RATE CONSTANTS; ATOMIC OXYGEN; 584 K;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Science Citation Index Expanded
Citazioni:
70
Recensione:
Indirizzi per estratti:
Citazione:
I.W.M. Smith, "COLLISIONAL ENERGY-TRANSFER, INTRAMOLECULAR VIBRATIONAL-RELAXATION AND UNIMOLECULAR REACTIONS", Journal of the Chemical Society. Faraday transactions, 93(21), 1997, pp. 3741-3750

Abstract

Experiments on (a) association reactions at very high pressures and (b) vibrational relaxation between species capable of forming a strong chemical bond have confined the hypothesis that, for the same chemicalsystem, these two rates are essentially the same, both reflecting therate of formation of collision complexes. The results of these measurements are reviewed. Subsequently, cases are discussed where the attraction between the collision partners is less strong. In these cases, it seems that the vibrational relaxation rate corresponds to a lower limit for complex formation, as complexes formed in collisions involvinga vibrationally excited species may redissociate before intramolecular vibrational relaxation within the complex randomises the energy located in the initially excited vibration. A number of examples, CH + N-2, NO +/- NO2, NO + NO, several ion-molecule systems and several involving OH and unsaturated molecules, where this behaviour seems to be occurring are discussed. It is emphasised that, whether or not the limiting, 'strong attraction', behaviour is observed will depend on the energy of the colliding species and therefore, in thermal experiments, on temperature. Finally, some consideration is given to the state-to-state aspects of vibrational energy transfer in collisions proceeding via collision complexes.

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Documento generato il 21/09/20 alle ore 12:31:59