Coincidence Studies of Exotic Anions and Reactive Intermediates

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In this award, funded by the Experimental Physical Chemistry program, Robert Continetti of the University of California, San Diego and his students are studying the energetics and dynamics of double-Rydberg anions, dipole-bound anions, and anionic precursors to systems involved in biological and atmospheric processes. The experiments exploit photoelectron-photofragment coincidence (PPC) spectroscopy, a powerful technique developed by the Continetti group. Studies of the double-Rydberg species probe fundamental questions relating to the correlation of pairs of electrons moving in diffuse orbitals. Continetti and his group also will study water cluster anions and weakly bound clusters of the hyponitrite ion (NO-) with water, ammonia, and hydrogen sulfide. These studies will provide an improved understanding of the solvation of NO- and of nitric oxide (NO), which plays an important role in the regulation of blood flow. The experimental work is supported by electronic structure calculations on the energetics and dynamics of the photodissociation processes. Professor Kit Bowen of Johns Hopkins University, who has produced and characterized double-Rydberg anions using negative ion photoelectron spectroscopy, will support Continetti in this work. The experiments carried out by Continetti and his group using the PPC technique will lead to a deeper understanding of the electronic structures of several important anionic systems. These experiments are of considerable interest in theoretical and atmospheric chemistry, as well as having applications in biochemistry. The project will provide excellent training for graduate students and postdoctoral fellows in physical chemistry.