The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO(2) (2+) dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340+/-0.010 eV. The fragmentation of energy selected CO(2) (2+) ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from approximately 38.7 to approximately 41 eV above the ground state of neutral CO(2) has been observed in the experimental time window of approximately 0.1-2.3 mus with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO(+)+O(+) formation in indirect dissociative double photoionization below the threshold for formation of CO(2) (2+). The threshold for CO(+)+O(+) formation is found to be 35.56+/-0.10 eV or lower, which is more than 2 eV lower than previous measurements.

Two Auger electrons, one very slow, one fast, have been detected in coincidence following near threshold 4d photoionization of the Xe atom. The distribution in the energy the two electrons share has been measured for the first time revealing the presence of post-collision interaction effects that provide unique information on the decay dynamics of the 4d hole. Analysis of the distorted line shapes indicates that the dominant process is decay of Xe+(4d(-1)) to Xe3+ through cascade emission of a zero kinetic energy Auger electron followed by a fast Auger electron. The widths of the intermediate Xe2+* states are estimated to be about 60 meV.

Formation of fluorescing and metastable fragments from photon-induced dissociation of O2 has been investigated in the 20.2–21.2 eV and 22.5–25.0 eV photon energy regions under high resolution. The neutral particles are detected using a microchannel plate stack, where electric potentials prevent charged particles from reaching the detector. Yield curves of excited neutral particles exhibit peaks at Rydberg states converging to O2+(B 2Σg−) and O2+(c 4Σu−). Furthermore, these yields are strongly enhanced at high-n, enabling the measurement of their energy location and width. A simple model for the decay of the Rydberg states converging to O2+(c 4Σu−) based on the competition between autoionization and neutral dissociation is used to describe qualitatively the observed spectrum. The results indicate that the lifetime of the O2+(c 4Σu−)v = 0 level is two orders of magnitude longer than that of the O2+(c 4Σu−)v = 1 level.

The photodetachment of a triatomic negative ion is studied and the detached-electron wave function is obtained as a superposition of coherent waves originating from each atom of the system. The photodetached electron flux is evaluated on a screen placed at a large distance from the system, which displays strong interferences. A simple analytical formula is also obtained for the total photodetachment cross section. The formula approaches one time the cross sections for the one-center and two-center systems in the high photon energy limits. Also it approaches three times the cross section for one-center system in the low photon energy limits.