Variational transition state analysis was performed on the barrierless phenyl + O-2 and phenoxy + O association reactions. In addition, we also calculated rate constants for the related vinyl radical (C2H3) + O-2 and vinoxy radical (C2H3O) + O reactions and provided rate constant estimates for analogous reactions in substituted aromatic systems. Potential energy scans along the dissociating C-OO and CO-O bonds (with consideration of C-OO internal rotation) were obtained at the O3LYP/6-31G(d) density functional theory level. The CO-O and C-OO bond scission reactions were observed to be barrierless, in both phenyl and vinyl systems. Potential energy wells were scaled by G3B3 reaction enthalpies to obtain accurate activation enthalpies. Frequency calculations were performed for all reactants and products and at points along the potential energy surfaces, allowing us to evaluate thermochemical properties as a function of temperature according to the principles of statistical mechanics and the rigid rotor harmonic oscillator (RRHO) approximation. The low-frequency vibrational modes corresponding to R-OO internal rotation were omitted from the RRHO analysis and replaced with a hindered internal rotor analysis using O3LYP/6-31 G(d) rotor potentials. Rate constants were calculated as a function of temperature (300-2000 K) and position from activation entropies and enthalpies, according to canonical transition state theory; these rate constants were minimized with respect to position to obtain variational rate constants as a function of temperature. For the phenyl + O-2 reaction, we identified the transition state to be located at a C-OO bond length of between 2.56 and 2.16 angstrom (300-2000 K), while for the phenoxy + O reaction, the transition state was located at a CO-O bond length of 2.00-1.90 angstrom. Variational rate constants were fit to a three-parameter form of the Arrhenius equation, and for the phenyl + O-2 association reaction, we found k(T) 1.860 x 10(13)T(-0.217) exp(0.358/7) (with k in cm(3) mol(-1) s(-1) and T in K); this rate equation provides good agreement with low-temperature experimental measurements of the phenyl + O-2 rate constant. Preliminary results were presented for a correlation between activation energy (or reaction enthalpy) and pre-exponential factor for heterolytic O-O bond scission reactions.