The Role of Reactant Vibrational Excitation in Transition Metal Chemistry

Cornell University, Ithaca NY

Investigators

Abstract

In this project, funded by the Experimental Physical Chemistry Program of the Chemistry Division, Davis will investigate the role of reactant vibrational energy in carbon-hydrogen and carbon-carbon bond activation reactions involving ground state neutral transition metal atoms and small unsaturated transition metal complexes. Direct infrared vibrational excitation or stimulated Raman pumping (SRP) for state-selective preparation of reactants will be employed. Bimolecular and unimolecular reactions will be studied. Angular and velocity distributions will be determined using crossed molecular beams and 157 nm ultraviolet radiation to photoionize neutral reaction products. Vibrational overtone induced unimolecular decomposition of volatile transition metal monomer, as well as binary complexes will be investigated. Chemical changes in normally unreactive hydrocarbon bonds facilitated by transition metal centers is of great importance in industrial catalytic processes and in organic and organometallic synthesis. The research done in this project will provide important benchmark information for tests of state-of-the-art theoretical and dynamic methods applied to bond activation reactions. Graduate and undergraduate students will participate in this research. They will be prepared for advanced studies or employment in academia, industry, or government laboratories.