Hole-filling spectroscopy of the \textit{trans}-formanilide-H$_{2}$O and tryptamine-H$_{2}$O complexes: Solvent shuttling and solvent loss

Studies of molecular clusters formed and cooled in a supersonic expansion offer unique opportunities to study novel types of dynamical processes under well-defined conditions. This talk will highlight recent studies in our laboratory at Purdue involving water-containing complexes with \textit{trans}-formanilide (TFA) and tryptamine (TRA). In TFA-H$_{2}$O, stimulated emission pumping is used to initiate a unique type of reaction in which a single water molecule is shuttled between remote hydrogen-bonding sites on the same solute molecule. The energy barrier to isomerization is measured for shuttling the molecule in either direction. In TRA-H$_{2}$O and TRA(ND$_{2})$-D$_{2}$O, infrared excitation is used to dissociate the water molecule from a flexible molecule with well-defined starting geometry. Isomer-specific product quantum yields of the TRA monomer product will be reported as a function of the XH or XD oscillator excited. The interplay between water loss and conformational isomerization of the flexible TRA molecule will be discussed.