Accurate isomeric energy differences and standard enthalpies of formation for disputed intermediates in soot formation, C4H3 and C4H5, have been determined through systematic extrapolations of ab initio energies. Electron correlation has been included through second-order Z-averaged perturbation theory (ZAPT2), and spin-restricted, open-shell coupled-cluster methods through triple excitations [ROCCSD, ROCCSD(T), and ROCCSDT] utilizing the correlation-consistent hierarchy of basis sets, cc-pVXZ (X=D, T, Q, 5, and 6), followed by extrapolations to the complete basis set limit via the focal point method of Allen and co-workers. Reference geometries were fully optimized at the ROCCSD(T) level with a TZ(2d1f,2p1d) basis set. Our analysis finds that the resonance-stabilized i-C4H3 and i-C4H5 isomers lie 11.8 and 10.7 kcal mol(-1) below E-n-C4H3 and E-n-C4H5, respectively, several kcal mol(-1) (more, less) than reported in recent (diffusion Monte Carlo, B3LYP density-functional) studies. Moreover, in these systems Gaussian-3 (G3) theory suffers from large spin contamination in electronic wave functions, poor reference geometries, and anomalous vibrational frequencies, but fortuitous cancellation of these sizable errors leads to isomerization energies apparently accurate to 1 kcal mol(-1). Using focal-point extrapolations for isodesmic reactions, we determine the enthalpies of formation (Delta(f)H(0)degrees) for i-C4H3, Z-n-C4H3, E-n-C4H3, i-C4H5, Z-n-C4H5, and E-n-C4H5 to be 119.0, 130.8, 130.8, 78.4, 89.7, and 89.1 kcal mol(-1), respectively. These definitive values remove any remaining uncertainty surrounding the thermochemistry of these isomers in combustion models, allowing for better assessment of whether even-carbon pathways contribute to soot formation. (C) 2004 American Institute of Physics.