Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2011-12-29

Characterizing the rovibrational distribution of CD2CD2OH radicals produced via the photodissociation of 2-bromoethanol-d4.

Caroline C Womack, Ryan S Booth, Matthew D Brynteson, Laurie J Butler, David E Szpunar

Index: J. Phys. Chem. A 115(51) , 14559-69, (2011)

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Abstract

This work characterizes the internal energy distribution of the CD(2)CD(2)OH radical formed via photodissociation of 2-bromoethanol-d(4). The CD(2)CD(2)OH radical is the first radical adduct in the addition of the hydroxyl radical to C(2)D(4) and the product branching of the OH + C(2)D(4) reaction is dependent on the total internal energy of this adduct and how that energy is partitioned between rotation and vibration. Using a combination of a velocity map imaging apparatus and a crossed laser-molecular beam scattering apparatus, we photodissociate the BrCD(2)CD(2)OH precursor at 193 nm and measure the velocity distributions of the Br atoms, resolving the Br((2)P(1/2)) and Br((2)P(3/2)) states with [2 + 1] resonance enhanced multiphoton ionization (REMPI) on the imaging apparatus. We also detect the velocity distribution of the subset of the nascent momentum-matched CD(2)CD(2)OH cofragments that are formed stable to subsequent dissociation. Invoking conservation of momentum and conservation of energy and a recently developed impulsive model, we determine the vibrational energy distribution of the nascent CD(2)CD(2)OH radicals from the measured velocity distributions.© 2011 American Chemical Society