Web Release Date: February 27,
Transition State Resonances in the Reaction Cl + H2 
HCl + H
Received: November 30, 1998 In Final Form: January 11, 1999 Abstract: This paper discusses converged quantum mechanical scattering calculations for the reaction Cl + H2 Download the full text:
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and HCl
+ H and its reverse and analyzes them for the properties of quantized dynamical bottlenecks controlling the
total and state-specific microcanonical-ensemble rate constants. These rate constants show clear evidence for
quantized transition states. We assign bend and stretch quantum numbers to the transition states for total
angular momentum J = 0 with parity P = +1, for J = 1 with P = +1 and -1, and for J = 2 and 6 with P
= +1. Then, state-specific densities of reactive states (transition state spectra) are examined to obtain a detailed
picture of the reaction. A quantal estimate of the rotational constant, B, for several different transition states
is obtained by comparing transition state energies at different values of the total angular momentum. These
quantal estimates are in good agreement with the values calculated from the moments of inertia, and this
enables us to interpret the results in terms of state-dependent geometries for the individual dynamical
bottlenecks. By treating the transition states as poles in the scattering matrix, we also obtain estimates for the
lifetimes of the states. The JP-specific rate coefficients, the reactant-state-specific rate coefficients, and the
contribution from each transition state to the JP-specific and the reactant-state-specified rate coefficient are
also calculated and the trends analyzed. These trends help explain the dependence of the rate coefficient on
initial vibrational and rotational quantum numbers.
