Dynamical resonances in the fluorine atom reaction with the hydrogen molecule

The concept of transition state has played a crucial role in the field of chemical kinetics and reaction dynamics. Resonances in the transition state region are important in many,chemical reactions at reaction energies near the thresholds. Detecting and characterizing isolated reaction resonances, however, have been a major challenge in both experiment and theory. In this Account, we review the most recent developments in the study of reaction resonances in the benchmark F + H-2 -> HF + H reaction. Crossed molecular beam scattering experiments on the F + H-2 reaction have been carried out recently using the high-resolution, highly sensitive H-atom Rydberg tagging technique with HF rovibrational states almost fully resolved. Pronounced forward scattering for the HF (nu' = 2) product has been observed at the collision energy of 0.52 kcal/mol in the F + H-2 (j = 0) reaction. Quantum dynamical calculations based on two new potential energy surfaces, the Xu-Xie-Zhang (XXZ) surface and the Fu-Xu-Zhang (FXZ) surface, show that the observed forward scattering of HF (nu' = 2) in the F + H-2 reaction is caused by two Feshbach resonances (the ground resonance and first excited resonance). More interestingly, the pronounced forward scattering of HF (nu' = 2) at 0.52 kcal/mol is enhanced considerably by the constructive interference between the two resonances. In order to probe the resonance potential more accurately, the isotope substituted F + HD -> HF + D reaction has been studied using the D-atom Rydberg tagging technique. A remarkable and fast changing dynamical picture has been mapped out in the collision energy range of 0.3-1.2 kcal/mol for this reaction. Quantum dynamical calculations based on the XXZ surface suggest that the ground resonance on this potential is too high in comparison with the experimental results of the F + HD reaction. However, quantum scattering calculations on the FXZ surface can reproduce nearly quantitatively the resonance picture of the F + HD reaction observed in the experiment. It is dear that the dynamics of the F + HD reaction below the threshold was dominated by the ground resonance state. Furthermore, the forward scattering HF (nu' = 3) channel from the F + H-2 (j = 0) reaction was investigated and was attributed mainly to a slow-down mechanism over the centrifugal exit barrier, with small contributions from a shape resonance mechanism in a narrow collision energy range. A striking effect of the reagent rotational excitation on resonance was also observed in F + H-2 (j = 1), in comparison with F + H-2 (j = 0). From these concerted experimental and theoretical studies, a clear physical picture of the reaction resonances in this benchmark reaction has emerged, providing a textbook example of dynamical resonances in elementary chemical reactions.