An improved potential energy surface for F+H2→HF+H and H+H′F→HF+H′

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Abstract
We present an improved analytic potential energy surface for the F+H2→FH+H and H+FH′→HF+H′ reactions. The final surface is obtained in two stages. First we create a surface, called No. 4, which is based in the F–H–H barrier region on a previous partly empirical and partly theoretical fit and is based on the F–H⋅⋅⋅H exit channel and H–F–H barrier regions on new large‐basis‐set configuration interaction calculations. The final surface, called No. 5 incorporates more empirical information for collinear geometries in both the F–H–H and FH⋅⋅⋅H regions but remains a good representation of the ab initio calculations for bending potentials and in the strong‐interaction regions. Variational‐transition‐state theory rate constants and WKB adiabatic barrier heights indicate that the final surface is more accurate than previous surfaces for thermal rate constants and overall reaction thresholds for F+H2→HF+H, F+D2→DF+D, and F+HD→HF+D and for product‐state thresholds for HF (n′=3) and DF(n′=4), where n′ is the final vibrational quantum number.

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