Molecular Structure and Dynamics beyond the Born-OppenheimerApproximation

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The Experimental Physical Chemistry Program supports Professor Grant in a continuing experimental and theoretical study of bound-state surface intersections and their effects upon excited-state dynamics in isolated molecules. The purpose of the work is to develop a more complete understanding of the consequences of coupling betwen electronic and nuclear motion in isolated molecules and complexes. The vibrational structure of intramolecular potential surface intersections is being studied experimentally in molecular beams pumped by lasers and probed by ionization-detected Rydberg absorption spectroscopy and zero-kinetic-energy photoelectron spectroscopy. Systems being investigated include various triatomics and polyatomics; multiresonant techniques can give resolution to a vibrational-rotational level of detail. Theoretical work is extending existing capabilities for handling large diagonalizations to allow the solving of three-state multimode problems. Techniques are also being developed to derive classical analogs for radiationless dynamics of vibronically-mixed valence states of excited triatomics. Berry's phase is also being investigated in extended parameter spaces.