Quasi-Classical Trajectory Study of the F + D2 .fwdarw. DF + D Reaction on a New ab Initio Potential Energy Surface. Comparison with Molecular Beam Experimental Results

Abstract

The F + D2 reaction dynamics has been studied by means of quasi-classical trajectory calculations on a new a b initio potential energy surface. In general, there is a remarkably good agreement between the calculated and experimental vibrationally resolved differential and integral cross sections for all the collision energies studied experimentally. As in the experiments, production of DF in the v' = 3 vibrational state dominates, with smaller fractions in v' = 1, v' = 2, and v' = 4. A forward peak appears selectively for v' = 4 at the highest collision energy, in good accordance with the experimental findings.

“Direct” Calculation of Thermal Rate Constants for the F + H2 → HF + F Reaction

“…Several other dynamics calculations have been carried out on this same Stark-Werner (SW) surface, including quasiclassical trajectory 41 and quantum scattering studies. 42 We refer the reader to the recent excellent review by Manolopoulos 22 on this reaction.…”

Observation of a transition state resonance in the integral cross section of the F+HD reaction

“…4 The evidence for reactive resonances in the beam experiments was not conclusive, however, since there are other dynamical explanations for the forward scattering peak when considered on the realistic potential surface. 5,6 Furthermore, the contemporaneous theoretical simulations could not reproduce the experimental results in a way that would confirm the existence of a resonance. Nevertheless, since this work, it has become the conventional wisdom that resonances should be sought in the differential cross section for collision experiments since impact parameter averaging is expected to smear out resonance features in the total reactive cross section.…”

Cumulative reaction probabilities and transition state properties: A study of the F+H2 reaction and its deuterated isotopic variants

“…This reactive system has received a great deal of attention over the last four decades. 11 Quantum mechanical ͑QM͒ and quasiclassical trajectory ͑QCT͒ calculations of integral and DCS and rate constants on the SW-PES could reproduce the available experimental data with comparatively small discrepancies, [12][13][14][15][16][17][18][19] and the resonance interpretation of the forward peaks observed in the experiments of Lee and coworkers was questioned. In the 1980s, the landmark experiments of Lee and co-workers 3,4 provided the vibrationally state-resolved differential cross sections ͑DCSs͒ for F + H 2 and its deuterated isotopic variants.…”