Spectral analysis and photofragmentation dynamics of the perdeuteromethoxy radical

The (A) over tilde(2)A(1)-(X) over tilde(2)E electronic spectrum of the CD3O radical has been investigated in detail. By using a variety of techniques, including rotational structure analysis. over 65 bands terminating on different vibronic levels of the A state have been assigned. The branching ratios for fluorescence decay vs photofragmentation of these same levels have also been determined. The detailed spectroscopic mapping of the A state vibronic structure is used to interpret the dynamical observations. The fragmentation is Found to be rather mode specific, with upsilon(3), the C-O stretch, being a major promoting mode, while upsilon(2), the umbrella motion, is not. Unexpectedly the methyl rock, upsilon(6), also appears to be an affective promoting mode.