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Titolo:
STATISTICAL AND DYNAMICAL BEHAVIOR IN THE UNIMOLECULAR REACTION DYNAMICS OF POLYATOMIC-MOLECULES
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:
0166-1280(1996)368:<125:SADBIT>2.0.ZU;2-P
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRANSITION-STATE THEORY; BOND FISSION REACTIONS; METHYL ISOCYANIDE; RATE CONSTANTS; ISOMERIZATION; 1,2-DIFLUOROETHANE; 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 POLYATOMIC-MOLECULES", Journal of molecular structure. Theochem, 368, 1996, pp. 125-131

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 non-statistical. 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 non-statistical behaviour in the subsequent unimolecular reaction dynamics of locally and microcanonically excited polyatomic molecules.

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Documento generato il 09/07/20 alle ore 01:42:32