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Physical Chemistry Chemical Physics
Article . 1999 . Peer-reviewed
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Quantum-mechanical statistical theories for chemical reactivity: overlapping resonances

Authors: Desouter, Michèle; Chapuisat, Xavier;

Quantum-mechanical statistical theories for chemical reactivity: overlapping resonances

Abstract

A unified analysis of the link between the statistical concept of microcanonical reaction rate constant and the collisional concepts of resonance width and resonance overlap is presented. It allows one to propose an interpretation to a recent controversy, according to which the transition state theory rate constant saturates, either when the discrete-continuum coupling terms increase and the transmission coefficients individually tend to one (Peskin, Reisler and Miller, J. Chem. Phys., 1997, 106, 4812), or when the increase of the discrete-continuum coupling terms induces the saturation of the mean resonance width because of the trapping effect (Rotter, J. Chem. Phys., 1997, 106, 4810). Both proposals may be true, depending on which definition of the resonance widths, energy gaps and resonance overlaps the discussion is referred to: either from the zero-order discrete states, whose widths are perturbationally estimated at the level of the golden rule, or from a set of narrow resonances appearing as a consequence of the trapping effect. In the unified interpretation, important roles are played by the penetration matrix of Satchler (Phys. Lett., 1963, 7, 55) and by the correlation width of Moldauer (Phys. Rev. C, 1974, 11, 426), two ingredients often used in nuclear physics literature.

Country
Belgium
Related Organizations
Keywords

Chemistry, Physical, chemical, mathematical & earth Sciences, Physique, chimie, mathématiques & sciences de la terre, Chimie

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
23
Average
Top 10%
Top 10%
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