Accurate three-dimensional time-dependent quantum wave packet calculations for the NϩOH reaction on the 3 AЉ potential energy surface ͓Guadagnini, Schatz, and Walch, J. Chem. Phys. 102, 774 ͑1995͔͒ have been carried out. The calculations show for the first time that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The calculated reaction cross sections indicate that they are a decreasing function of the translational energy, which is in agreement qualitatively with the quasiclassical trajectory calculations. The rate constants obtained from the quantum mechanical calculations are consistent with the quasiclassical trajectory results and the experimental measurements.
Three-dimensional time-dependent quantum wave packet calculation was carried out to study the dynamics of the C + CH reaction on the 2A′ potential energy surface. The energy dependence of the calculated total reaction probabilities exhibits no long-lived resonance despite the presence of a deep well, a feature similar to that on the 1A 2 surface. The effect of initial vibrational and rotational excitation of the reagent on reactivity is investigated, and the reaction rate constants and integral cross sections are calculated and compared with quasiclassical trajectory results. This study shows that results of the quantum calculation are generally in good agreement with the QCT results and the difference is relatively small. The analysis of stereodynamics indicates that the C + CH reaction could occur within a wide range of the attack angle. The C side of the product CH (molecule or radical) is the slight favorite side for the reactive attack.
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