Interferences in coherent emission of photoelectrons from two equivalent atomic centers in a molecule are the microscopic analogies of the celebrated Young's double-slit experiment. By considering inner-valence shell ionization in the series of simple hydrocarbons C2H2, C2H4, and C2H6, we show that double-slit interference is widespread and has built-in quantitative information on geometry, orbital composition, and many-body effects. A theoretical and experimental study is presented over the photon energy range of 70-700 eV. A strong dependence of the oscillation period on the C-C distance is observed, which can be used to determine bond lengths between selected pairs of equivalent atoms with an accuracy of at least 0.01 Å. Furthermore, we show that the observed oscillations are directly informative of the nature and atomic composition of the inner-valence molecular orbitals and that observed ratios are quantitative measures of elusive many-body effects. The technique and analysis can be immediately extended to a large class of compounds.
Keywords: coherent state and molecular photoemission; interference phenomena.