Imaging Dynamics on the F + H2O → HF + OH Potential Energy Surfaces from Wells to Barriers

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Science  24 Jan 2014:
Vol. 343, Issue 6169, pp. 396-399
DOI: 10.1126/science.1247424

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The study of gas-phase reaction dynamics has advanced to a point where four-atom reactions are the proving ground for detailed comparisons between experiment and theory. Here, a combined experimental and theoretical study of the dissociation dynamics of the tetra-atomic FH2O system is presented, providing snapshots of the F + H2O → HF + OH reaction. Photoelectron-photofragment coincidence measurements of the dissociative photodetachment (DPD) of the F¯(H2O) anion revealed various dissociation pathways along different electronic states. A distinct photoelectron spectrum of stable FH–OH complexes was also measured and attributed to long-lived Feshbach resonances. Comparison to full-dimensional quantum calculations confirms the sensitivity of the DPD measurements to the subtle dynamics on the low-lying FH2O potential energy surfaces over a wide range of nuclear configurations and energies.

A View from the Middle

The intuitive way to study a bimolecular reaction is to induce a collision between separate reagents and then track the ensuing events. Crossed molecular beam studies have revealed the quantum mechanical details of numerous systems in this fashion. Otto et al. (p. 396, published online 9 January) applied a more recent approach of starting in the middle of the F + H2O → HF + OH reaction trajectory, postcollision, by photodetaching an electron from a stabilized complex of water and a fluoride ion, and then tracking the fate of the neutral fragments.

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