This project, supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program, involves a combined experimental and theoretical study of the photochemical reactions of a variety of dinuclear metal carbonyl complexes. The objective of the study is to develop a detailed understanding of the elementary processes that accompany absorption of a photon by the organometallic molecule and how these are affected by changes in the ligands. The research will proceed with conventional preparative scale photolyses, matrix isolation, and flash photolysis studies of several series of dinuclear compounds in which the bridging ligands, terminal ligands and metal atoms are varied. These studies will be followed by detailed, ultrafast laser studies designed to probe the elementary processes. In addition to monitoring by conventional visible spectroscopy, picosecond, transient Raman scattering and infrared techniques will also be used in order to obtain structural information concerning transient intermediates. Finally, molecular dynamics will be modeled via theoretical electronic structure calculations using both approximate and ab initio computational methods. %%% This research is designed to experimentally and theoretically investigate events that occur extremely rapidly following absorption of a photon by an organometallic compound. Through the combination of experimental and theoretical studies to be utilized it is expected that our understanding of these events will develop to the point that in the future predictions can be made about how the reactivity of an organometallic compound will be affected by changes in the groups attached to the metal atom. Ultimately these results may be important in the synthesis of new materials and in the design of new catalysts.
