The near ultraviolet photolysis of jet‐cooled acetylene molecules has been further investigated using the technique of H atom photofragment translational spectroscopy. Analysis of the rotational structure evident in the total fragment kinetic energy spectrum yields a precise value for the C–H bond dissociation energy: D0(HCC–H)=46 074±8 cm−1 (551.2±0.1kJ mol−1).

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