A New Strategy for Vibronic Spectroscopy of Radicals

ongoing

This proposal aims to develop a novel strategy for high resolution vibronic spectroscopy of radicals, with unprecedented sensitivity, specificity, and applicability. The proposed scheme will provide answers to longstanding quantum mechanical questions about non-adiabatic dynamics, and, in combination with a unique, recently developed transparent microreactor source of reactive molecules, enable the pursuit of unknown reactive intermediates. Radicals and transient reactive intermediates are centrally important to chemistry but notoriously difficult to study. The proposer has recently led several successful experimental and theoretical efforts directed at molecules and transition states thought to be extremely difficult if not impossible to characterize. Here we propose to launch a revolutionary approach to spectroscopy of these important species, exploiting a key insight into dissociation dynamics on top of elements of state of the art laser spectroscopy techniques in the infrared, ultraviolet, and vacuum ultraviolet to forge a new universal method. It possesses the high sensitivity and mass selectivity of ion detection, while simultaneously being multidimensional and fully rovibronic in scope to extract the maximum possible information about coupled nuclear and electronic dynamics. We anticipate that this advance will also be of great interest and utility to a broad swath of researchers in related fields, such as combustion, atmospheric chemistry, and surface science, who require the ability to track rare but reactive species. The nitrate and cyclopentadienyl radicals will initially be targeted as particularly important examples, and we also plan to hunt for as yet unobserved reactive intermediates using our new spectroscopic scheme alongside the flexibility of our molecular source to rationally explore chemical phase space.