Selective Bond Breaking in CO_{2}^{2+} Induced by Photoelectron Recoil

After core ionization of CO_{2}, typically an Auger-Meitner decay takes place, leading to the formation of a dicationic molecule that may dissociate into CO^{+} and O^{+}. We demonstrate experimentally that the recoil momentum of the photoelectron determines which of the two equivalent bonds breaks during dissociation. At 20 keV photon energy, we observe an asymmetry of up to 25% for bond cleavage that depends on the emission direction of the photoelectron. Furthermore, we show that this effect leads to a significant nondipole effect in molecular dissociation in the laboratory frame: O^{+} fragments are more likely to be emitted in the direction opposite to the light propagation than along it.