Spectroscopy of radicals in condensed phase
Take it or leave it, but real chemistry does happen in condensed phases! In particular, aqueous radicals are implicated in atmospheric chemistry (HOO, ClO, NO3), radiation chemistry (water coolant in nuclear reactors), and enzymatic processes (Tyr).
Experiments in Bradforth lab utilize ultrafast laser techniques to investigate the coupling between the solvent and solute in ICN photodissociation. The interpretation of the data heavily depends on the spectral assignment of transient species present of the solution. Of special interest is the CN radical, for which conflicting spectral assignments appeared in literature.
Electronic structure of open-shell species in water is a theoretically
difficult problem due to (i) large size of the system, (ii) high level of
theory required for their proper description. The avenue to progress lead
via a combination of classical molecular dynamics and electrostatic
treatment of water. The study revealed an expected blue shift of the