Experimental Characterization of Idealized Metal-Centered Reactions Darrin Bellert Baylor University Zach Theis Adam Mansell Katie Benjamin Research Problem: Catalysis is not well understood. The complex nature of the catalytic systems environment makes resolved study nearly impossible. Therefore, to better understand the catalytic process, we have designed an experiment where environmental parameters are either removed or specified. Experiment: -ionic clusters, cooled in supersonic expansion -A quantum of laser photon energy provides reaction activation energy -Selective detection of fragment ions -Direct measurement of reaction kinetic parameters Ni + (Butanone) Co + (Acetone) Custom Sector Hemispherical, kinetic energy analyzer More on photon absorption, next slide Ni + -C-O Ni + C 3 H 4 O Energy Reaction Coordinate + CH 3 OH TS 2 EC I1I1 I2I2 TS 1 + C 2 H 4 The cation assisted decomposition of propanol An absorbed photon provides the activation energy required to drive the reaction to products. Two-photon absorption results in the entropic product, separated reactants that do not add to our product ion yield. Absorption of a quantum of photon energy provides the internal energy of the cluster, but how is this photon absorbed? Photon absorption is to a state with different multiplicity. Intersystem crossing to the low-spin state deposits the photons energy high into the vibrational levels of the ground state, providing the energy to surmount the kinetic barriers along the reaction coordinate Thus, the quantum of photon energy approximates the internal energy of the cluster. This technique allows us to measure the reaction kinetics, extracting k(E) values at well defined levels of cluster internal energy. In Summary, Instrumentation has been developed to generate reactants as a cold binary cluster in a laser-driven supersonic expansion introduce a resolved aliquot of energy to induce rearrangement dissociation selectively monitor fragment production in real time directly extract reaction rate constants from the unimolecular decay wave-forms extract dynamical information from the H/D kinetic isotope effect And finally The difference between Physical Chemists and Organic Chemists Questions?