Rydberg Structure and Dynamics of Highly Excited Small Molecules

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Edward Grant of Purdue University is supported by a grant from the Experimental Physical Chemistry Program to continue his experimental research on state-to-state photoionization and dynamics of intramolecular relaxation by rovibronic coupling in highly excited (Rydberg) states of small molecules. These experiments will be accomplished by multi-photon resonant ionization and high-resolution threshold photoelectron spectroscopy, in particular, Zero Electron Kinetic Energy-Photoelectron Spectroscopy. The experiments will be paralleled by Multi-Channel Quantum Defect Theory calculations to identify highly excited rovibrational states and l coupling in these systems. These calculations, initiated by the PI, will be extended by a collaboration with a theorist who is expert in this area. Initially studies on the formyl radical and nitrogen dioxide will be continued, but these will be expanded to include other larger polyatomic molecules which are theoretically more challenging.Small reactive radical molecules in excited states are critical species in many chemical and physical processes occurring in media such as internal combustion, plasma processing, polluted atmospheres and the interstellar medium. In order to understand the molecular structure of, and energy transfer in, these species high resolution spectroscopy and high level theoretical calculations will be made. This will enable observation of these media to be interpreted and the media to be modeled.