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Titolo: STATISTICAL AND DYNAMICAL BEHAVIOR IN THE UNIMOLECULAR REACTION DYNAMICS OF POLYATOMICMOLECULES
Autore: SCHRANZ HW; SEWELL TD;
 Indirizzi:
 AUSTRALIAN NATL UNIV,RES SCH CHEM CANBERRA ACT 0200 AUSTRALIA LOS ALAMOS NATL LAB,DIV THEORET LOS ALAMOS NM 87545
 Titolo Testata:
 Journal of molecular structure. Theochem
,
volume: 368,
anno: 1996,
pagine: 125  131
 SICI:
 01661280(1996)368:<125:SADBIT>2.0.ZU;2P
 Fonte:
 ISI
 Lingua:
 ENG
 Soggetto:
 TRANSITIONSTATE THEORY; BOND FISSION REACTIONS; METHYL ISOCYANIDE; RATE CONSTANTS; ISOMERIZATION; 1,2DIFLUOROETHANE; DISILANE; CD2HNC; CH3NC;
 Keywords:
 UNIMOLECULAR REACTIONS; POLYATOMIC MOLECULE; INTRAMOLECULAR VIBRATIONAL ENERGY REDISTRIBUTION;
 Tipo documento:
 Article
 Natura:
 Periodico
 Settore Disciplinare:
 Science Citation Index Expanded
 Citazioni:
 22
 Recensione:
 Indirizzi per estratti:



 Citazione:
 H.W. Schranz e T.D. Sewell, "STATISTICAL AND DYNAMICAL BEHAVIOR IN THE UNIMOLECULAR REACTION DYNAMICS OF POLYATOMICMOLECULES", Journal of molecular structure. Theochem, 368, 1996, pp. 125131
Abstract
The dominant theories of unimolecular reaction are statistical. A fundamental assumption is that the timescale on which energy moves about a reactant molecule is much shorter than the timescale for reaction. It is assumed that intramolecular vibrational energy redistribution (IVR) is globally rapid throughout the molecular phase space. It has beenwidely thought that the assumption of rapid IVR referred to above is valid for sufficiently large polyatomics. Much of the supporting evidence for this view comes from indirect experimental studies of IVR and comparisons of statistical and dynamical calculations. However, the presence of a fast IVR rate, as derived from some experiments, does not automatically ensure the reaction dynamics will be statistical. In fact, in recent studies, we have shown that even in the presence of fast IVR rates between some modes the reaction dynamics can be extremely nonstatistical. Secondly, most comparisons of statistical and dynamicalcalculations have made simplifying assumptions which render the comparisons ambiguous. In the present paper, we investigate results of recent statistical and dynamical calculations performed on identical potential energy surfaces for a range of polyatomic molecules. Our ultimategoal is to determine how the extent and timescale of IVR plays a rolein determining the statistical or nonstatistical behaviour in the subsequent unimolecular reaction dynamics of locally and microcanonically excited polyatomic molecules.
ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 09/07/20 alle ore 01:42:32