Mechanisms of central O‐atom abstraction reactions: A molecular beam, laser‐induced fluorescence study of Group IIIB + ROH systems

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Abstract
The laser‐induced fluorescence method has been used to determine vibrational and rotational energy distributions of metal oxides formed in reactions of Group IIIB atoms with H2O, D2O, CH3OH, C2H5OH, iso‐C3H7OH, and n‐C3H7OH. The observation of metal oxide rather than metal hydroxide in these reactions can be explained using orbital symmetry arguments. Although no vibrational inversions are observed, the reaction of Y with D2O produces considerably less vibrational excitation of YO than the reaction with H2O, while alcohols give less vibrational and rotational excitation in YO for larger alkyl groups. The internal energy distributions are generally not in quantitative agreement with statistical expectations. In the case of the ethanol and propanol reactions agreement with statistical vibrational results is improved if fragmentation to three products is assumed, presumably via a concerted ring mechanism.

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