The spectroscopic characterization of the methoxy radical. II. Rotationally resolved A (2)A(1)-X (2)E electronic and X (2)E microwave spectra of the perdeuteromethoxy radical CD(3)O.

Rotationally resolved laser-induced fluorescence (LIF) and stimulated emission pumping (SEP) A (2)A(1)-X (2)E spectra of the perdeuteromethoxy radical (CD(3)O) have been observed. These data directly connect the two spin-orbit components (E(1/2) and E(3/2)) of the ground electronic state with high precision. Molecular constants for both electronic states are determined in a global fitting that involves LIF, SEP, and pure rotational spectra in the microwave region. For the microwave transitions, the resolved hyperfine structure is analyzed providing molecular parameters characterizing it and hyperfine-free transitions for the global fitting. A complete "experimental" geometry for the methoxy radical at the C(3v) conical intersection is determined from the rotational constants of its isotopologs. The experimental isotopic dependence of other parameters in the effective Hamiltonians is compared to the theoretically expected variation. These comparisons allow considerable insight into the physical significance of a number of parameters in the effective Hamiltonian. In particular, experimental evidence is found for a previously predicted vibrational correction to the A rotational constant of a Jahn-Teller active molecule.