Tunable laser photodissociation spectroscopy in the 700−400 nm region and photofragment imaging experiments are employed to investigate the Fe + (acetylene) ion−molecule complex. At energies above a threshold at 679 nm, continuous dissociation is detected throughout the visible wavelength region, with regions of broad structure. Comparison to the spectrum predicted by time-dependent density functional theory (TD-DFT) indicates that the complex has a quartet ground state. The dissociation threshold for Fe + (acetylene) at 679 nm provides the dissociation energy on the quartet potential energy surface. Correction for the atomic quartet−sextet spin state energy difference provides an adiabatic dissociation energy of 36.8 ± 0.2 kcal/ mol. Photofragment imaging of the Fe + photoproduct produced at 603.5 nm produces significant kinetic energy release (KER). The photon energy and the maximum value of the KER provide an upper limit on the dissociation energy of D 0 ≤ 34.6 ± 3.2 kcal/mol. The dissociation energies determined from the spectroscopy and photofragment imaging experiments agree nicely with the value determined previously by collision-induced dissociation (38.0 ± 2.6 kcal/mol). However, both values are significantly lower than those produced by computational chemistry at the DFT level using different functionals recommended for transition-metal chemistry.

Tunable laser photodissociation spectroscopy measurements and photofragment imaging experiments are employed to investigate the dissociation energy of the Fe+(benzene) ion–molecule complex. Additional spectroscopy measurements determine the dissociation energy of Fe+(benzene)2. The dissociation energies for Fe+(benzene) determined from the threshold for the appearance of the Fe+ fragment (48.4 ± 0.2 kcal/mol) and photofragment imaging (≤49.3 ± 3.2 kcal/mol) agree nicely with each other and with the value determined previously by collision-induced dissociation (49.5 ± 2.9 kcal/mol), but they are lower than the values produced by computational chemistry at the density functional theory level using different functionals recommended for transition-metal chemistry. The threshold measurement for Fe+(benzene)2 (43.0 ± 0.2 kcal/mol) likewise agrees with the value (44.7 ± 3.8 kcal/mol) from previous collision-induced dissociation measurements.

Ion–molecule complexes of uranium or thorium singly-charged positive ions bound to cyclooctatetraene (COT), i.e., M+(COT)1,2, are produced by laser ablation and studied with UV laser photodissociation. The ions are selected by mass and excited at 355 or 532 nm, and the ionized dissociation products are detected using a reflectron time-of-flight mass spectrometer. The abundant fragments M+(C6H6), M+(C4H4), and M+(C2H2) occur for complexes of both metals, whereas the M+(C4H2), M+(C3H3), and M+(C5H5) fragments are prominent for uranium complexes but not for thorium. Additional experiments investigate the dissociation of M+(benzene)1,2 ions which may be intermediates in the fragmentation of the COT ions. The experiments are complemented by computational quantum chemistry to investigate the structures and energetics of fragment ions. Various cation−π and metallacycle structures are indicated for different fragment ions. The metal ion–ligand bond energies for corresponding complex ions are systematically greater for the thorium species. The computed thermochemistry makes it possible to explain the mechanistic details of the photochemical fragmentation processes and to reveal new actinide organometallic structures.