Response to {open_quotes}Comment on {close_quote}On the relation between unimolecular reaction rates and overlapping resonances{close_quote}{close_quotes} [J. Chem. Phys. {bold 106}, 4810 (1997)]

Journal Article · Sat Mar 01 04:00:00 EST 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.473990· OSTI ID:467245

Peskin, U ^[1]; Reisler, H ^[2]; Miller, W H ^[3]

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1. Department of Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel)
2. Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)
3. Department of Chemistry, University of California and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States)

The unimolecular decay rate k(E) saturates with increasing bound-continuum coupling. This saturation was observed in various models including a random matrix version of the optical model. The phenomena was previously interpreted in terms the transition state theory for unimolecular decay. The mechanism for the saturation is associated with a broadening of the resonance widths distribution, but not with the {open_quotes}bifurcation{close_quotes} of the decay time scales into two groups as suggested by the {open_quotes}trapping effect.{close_quotes} The onset of the trapping effect within random matrix simulations leads to a nonphysical decrease of the effective decay rate with increasing bound continuum coupling. This nonphysical tendency is explained in terms of a physical inconsistent matrix approximation of the optical model for too large bound-continuum coupling. {copyright} {ital 1997 American Institute of Physics.}

• OSTI ID: 467245
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 106; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
BIFURCATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COUPLING
DECAY
RESONANCE
SATURATION
TRAPPING