Rovibrational photoionization dynamics of methyl and its isotopomers studied by high-resolution photoionization and photoelectron spectroscopy.

High-resolution photoionization and pulsed-field-ionization zero-kinetic-energy photoelectron spectra of CH(3), CH(2)D, CHD(2), and CD(3) have been recorded in the vicinity of the first adiabatic ionization threshold following single-photon excitation from the ground neutral state using a narrow-bandwidth vacuum-ultraviolet laser. The radicals were produced from the precursor molecules methyl-bromide, methyl-iodide, dimethyl-thioether, acetone, and nitromethane by 193 nm excimer photolysis in a quartz capillary and were subsequently cooled to a rotational temperature T(rot) approximately equal to 30 K in a supersonic expansion. Nitromethane was identified as a particularly suitable photolytic precursor of methyl for studies by photoionization and threshold photoelectron spectroscopy. Thanks to the cold rotational temperature reached in the supersonic expansion, the rotational structure of the threshold ionization spectra could be resolved, and the photoionization dynamics investigated. Rydberg series converging on excited rotational levels of CH(3) (+) could be observed in the range of principal quantum number n=30-50, and both rotational autoionization and predissociation were identified as decay processes in the threshold region. The observed photoionization transitions can be understood in the realm of an orbital model for direct ionization but the intensity distributions can only be fully accounted for if the rotational channel interactions mediated by the quadrupole of the cation are considered. Improved values of the adiabatic ionization thresholds were derived for all isotopomers [CH(3): 79 356.2(15) cm(-1), CH(2)D: 79 338.8(15) cm(-1), CHD(2): 79 319.1(15) cm(-1), and CD(3): 79 296.4(15) cm(-1)].