Journal of Chemical Physics, Vol.104, No.16, 6200-6207, 1996
Kinetic-Energy Release in the Dissociation of CO2(2+)
The kinetic-energy release distributions (KERDs) of the fragment ion pairs (O++CO+) and C++O+) produced in dissociative double photoionization of carbon dioxide have been determined by analyzing the photoion-photoion coincidence spectra measured in the region hv=40-100 eV by use of a time-of-flight mass spectrometer and synchrotron radiation. The mechanism of the three-body dissociation (CO22+-->C++O++O) has been examined to take place sequentially via CO+ by a triple photoelectron-photoion-photoion coincidence experiment. The KERD observed for the O++CO+ and C++O+ channels at low excitation energies cannot be explained by a simple framework whereby a doubly charged molecular ion (AB(2+)) is directly produced on single photon absorption followed by the dissociation of AB(2+) into two ionic fragments, Some of the ion pairs are produced through indirect processes in which highly excited CO2*(+) and CO2** (double Rydberg) states converging to the high-lying CO22+ electronic states autoionize before and after dissociation. From the observed KERDs for the O++CO+ and C++O+ channels of CO22+, the range of the intercharge distances of two positive holes is estimated by assuming that the KER is given purely by Coulomb repulsion.
Keywords:PHOTOION-PHOTOION COINCIDENCE;TRIPLE COINCIDENCE;AUGER-SPECTRA;PEPIPICO TECHNIQUE;MASS-SPECTROMETRY;DOUBLE IONIZATION;FRAGMENTATION;MOLECULES;DYNAMICS;IONS