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  • Title: Rotational, steric, and coriolis effects on the F + HCl --> HF + Cl reaction on the 1(2)A' ground-state surface.
    Author: Defazio P, Petrongolo C.
    Journal: J Phys Chem A; 2009 Apr 23; 113(16):4208-12. PubMed ID: 19371113.
    Abstract:
    We present a quantum study of the reaction F((2)P) + HCl(X(1)Sigma(+)) --> HF(X(1)Sigma(+)) + Cl((2)P) on a recently computed 1(2)A' ground-state surface, considering HCl in the ground vibrational state, with up to 16 rotational quanta j(0). We employ the real wavepacket (WP) and flux methods for calculating coupled-channel (CC) and centrifugal-sudden (CS) initial-state probabilities up to J = 80 and 140, respectively. We also report CC and CS ground-state cross sections and CS excited-state cross sections and discuss the dynamics analyzing WP time evolutions. The HCl rotation highly enhances reaction probabilities and cross sections, as it was previously found for probabilities at J </= 4. CS errors depend on j(0), on its z projection K(0), and on the collision energy and are small at j(0) = 0 and 16 but large at j(0) = 8. Differences between CC and CS results are associated with the reaction stereodynamics and energetics. Steric effects favor indeed the overcoming of the potential barrier and a linearly dominated mechanism. Attractive Coriolis couplings favor instead the energy flow from the HCl rotation to the F-H---Cl reactive vibration. WP snapshots confirm and explain the HCl rotational effects, because the density into the nearly collinear F-H---Cl product channel increases remarkably with j(0). Finally, our CS rate constant is underestimated with respect to the experiment, pointing out the need of more accurate multisurface and CC calculations.
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