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Nonstatistical Reaction Dynamics
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DOI：10.1146/annurev-physchem-112519-110208.png)
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Abstract
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Nonstatistical dynamics is important formany chemical reactions. The Rice-Ramsperger-Kassel-Marcus (RRKM) theory of unimolecular kinetics assumes a reactant molecule maintains a statistical microcanonical ensemble of vibrational states during its dissociation so that its unimolecular dynamics are time independent. Such dynamics results when the reactant's atomic motion is chaotic or irregular. Intrinsic non-RRKM dynamics occurs when part of the reactant's phase space consists of quasiperiodic/regular motion and a bottleneck exists, so that the unimolecular rate constant is time dependent. Nonrandom excitation of a molecule may result in short-time apparent non-RRKM dynamics. For rotational activation, the 2J + 1 K levels for a particular J may be highly mixed, making K an active degree of freedom, or K may be a good quantum number and an adiabatic degree of freedom. Non-statistical dynamics is often important for bimolecular reactions and their intermediates and for product-energy partitioning of bimolecular and uni-molecular reactions. Post-transition state dynamics is often highly complex and nonstatistical.
Keywords:
non-RRKM unimolecular dynamics
product energy partitioning
post-transition state dynamics
nonstatistical reaction dynamics
nonintrinsic reaction coordinate dynamics
bimolecular reactions
reaction intermediates
S(N)2 reaction dynamics
phase space dynamics
rotational/vibrational coupling
active rotation
adiabatic rotation
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