Photoinitiated Reactions in Weakly Bonded Complexes

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The Experimental Physical Chemistry Program is continuing support of Professor Wittig in pioneering investigations of photoinitiated reactions within weakly-bonded gas-phase complexes. A hydrogen atom, departing a photodissociated molecule, reacts with the neighboring weakly-bonded molecule under initial conditions much more precisely defined than is the case in typical investigations of kinetic processes. Significant insight is potentially available concerning the detailed dynamics of the reaction process. For the light hydrogen atom momentarily trapped between the other photodissociation fragment and an initially van der Waals-bonded partner, Wittig is searching for possible dynamical resonances as a function of the initial photodissociation conditions. Other work uses the velocity aligned Doppler spectroscopy technique to characterize completely the product excitations, including correlations between product internal states, for hydrogen atom reactions with nitrous oxide. Extensions will also be made to allow the investigation of complexes involving radicals weakly bonded to molecules. Structures of the various complexes are being determined with supplementary high-resolution tunable diode laser spectroscopy measurements.