title: A study of resonance progressions in the F + HCl → Cl + HF reaction: a lifetime matrix analysis of pre-reactive and post-reactive collision complexes.
abstract: Quantum scattering calculations were performed for the F + HCl → Cl + HF reaction for total angular momentum J = 0-6 using an ab initio potential energy surface. Employing a time-independent algorithm on a very fine energy grid allowed the resolution of hundreds of narrow resonances with lifetimes in the picosecond range. The resonances were assigned to rotationally excited van der Waals complexes lying in the entrance and exit channels. Resonance peaks observed in the J = 0 calculation broke into multiplets for J > 0 corresponding to the range of allowed helicity states. The Smith lifetime matrix, Q(E), was used to efficiently extract the resonance properties. The largest eigenvalue of Q(E) was used for the position and total width, while the corresponding eigenvector was used to obtain the partial widths. A simple model based on the conventional treatment of rotationally excited van der Waals triatomics was used to predict the resonance spectrum to an accuracy of ~0.02 kcal∕mol. The model predicts the density of resonance states in good agreement with the exact scattering results.
authors: Institute of Atomic and Molecular Sciences, Academia Sinica, P.O. Box 23-166, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw
authors: Kaito
authors: K
authors: Takahashi
authors: Michael Y
authors: MY
authors: Hayes
authors: Rex T
authors: RT
authors: Skodje