A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF(2+), SnCl(2+), and SnO(2+) using ab initio computer calculations. The ground states of SnF(2+), SnCl(2+), and SnO(2+) are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF(2+) dissociates into Sn(2+) + F, the long range behaviour of the potential energy curves of SnCl(2+) and SnO(2+) is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T(e)) to form SnF(2+), SnCl(2+), and SnO(2+) from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO(2+) and SnF(2+) have been observed for prolonged oxygen ((16)O(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF(2)) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl(2+) has been detected for (16)O(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl(2)) powder. To our knowledge, SnF(2+) is a novel gas-phase molecule, whereas SnCl(2+) had been detected previously by electron-impact ionization mass spectrometry, and SnO(2+) had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems.