Rydberg states of atoms and molecules play an important role in the chemistry of the interstellar medium (ISM) through processes such as dissociative recombination, and a number of low-lying Rydberg states of small molecules have been spectroscopically identified in the ISM. We will discuss recent experimental and theoretical work in advancing the laboratory study of high Rydberg states of small molecules. In particular, we have recently developed optical-millimeter-wave stimulated Raman adiabatic passage (optical-mmW STIRAP), a new method of coherent population transfer to access high angular momentum Rydberg states amenable to high-resolution spectroscopic investigation. These high-resolution experiments not only inform understanding of the Rydberg levels of these molecules, but also report on the electric structure of the molecular ion-core. Theoretically, we have expanded our multi-channel quantum defect theory analysis of the model system CaF to investigate rates of vibrational autoionization, a process of fundamental importance in molecular ion reactivity.

Developments in high-resolution spectroscopy of Rydberg states of small molecules

256th National Meeting (2018)

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