SPECTROSCOPIC CHARACTERIZATION OF INDUCTIVE BINDING IN IONS

Molecular ions without conventional covalent bonds have been synthesized via supersonic adiabatic expansion and studied in a tandem time-of-flight mass spectrometer. Resonant laser photofragmentation of these ions reveal a wealth of vibrational and electronic structure previously unknown. The ground and excited state "bond" strengths of transition-metal rare-gas diatomic ions (MRg+) are determined spectroscopically. The vibrational structure of these diatomics has been analyzed using model metal rare-gas interatomic potential that incorporates only charge induced-dipole as the attractive force. This potential is used to predict the binding energy and structure of the MRg(n)+, n = 2-14, clusters. V+ is predicted to be four coordinate in its first "solvation shell" with Ar in accord with experimental observations. The dynamics of the MRg(n)+ ions is probed by classical trajectory analysis of a model many-body potential. An example demonstrates that the lowest energy structure of a cluster can be less important to its dynamical structure at finite temperature than higher-lying, lower-symmetry isomers. Resonant photodissociation spectroscopy is used to show the existence of the charge dipole bound V(OH2)+ in both ground and excited states.