Accurate calculations of carbon photoionization cross sections have been performed at the density functional level with the B-spline linear combination of atomic orbitals approach. The molecules considered are FCCH, , FCCCN, , , and . The variation of the branching ratios relative to inequivalent C ionizations have been evaluated from threshold to about 100 eV photoelectron kinetic energy. Large deviations from the statistical ratios are observed at low energies, which remain often significant several tens of eV above threshold. The importance of taking into account core branching ratios for peak deconvolution and quantitative analysis, as well as an additional tool for structural information, is pointed out. Strong shape resonant effects are found to largely cancel in branching ratios. Their nature and variation along the series is analyzed in the framework of excitations into valence orbitals.
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