Photofragmentation studies of mass-selected, partially-solvated anionic clusters are performed to investigate solvent-number specific perturbations to the dissociation dynamics of anionic chromophores. Two anion solutes are employed in the studies reported here: IBr- and the chemically-related ICN-. While the former has been the subject of earlier photodissociation studies, ICN- has not been studied previously. Replacing Br with CN allows the possibilities of isomerization to INC- and rotational excitation of a photofragment. Two quite different solvents, CO2 and Ar, are utilized in the experiments. The CO2 solvent is bound to the chromophore by ~200 meV. Its charge distribution gives rise to substantial electric quadrupole and higher moments that can modify the electronic structure of the solute ion. The Ar solvent is much more weakly bound to the solute (~50 meV), has no permanent multipole moments, and no possibility of rotational, vibrational or electronic excitation in the dissociation process. The contrasting photodissociation dynamics associated with the different combinations of these solutes and solvents reported in this Dissertation both provides new understanding and raises questions concerning photoprocesses in partially solvated ionic complexes.
CY - Boulder N2 -Photofragmentation studies of mass-selected, partially-solvated anionic clusters are performed to investigate solvent-number specific perturbations to the dissociation dynamics of anionic chromophores. Two anion solutes are employed in the studies reported here: IBr- and the chemically-related ICN-. While the former has been the subject of earlier photodissociation studies, ICN- has not been studied previously. Replacing Br with CN allows the possibilities of isomerization to INC- and rotational excitation of a photofragment. Two quite different solvents, CO2 and Ar, are utilized in the experiments. The CO2 solvent is bound to the chromophore by ~200 meV. Its charge distribution gives rise to substantial electric quadrupole and higher moments that can modify the electronic structure of the solute ion. The Ar solvent is much more weakly bound to the solute (~50 meV), has no permanent multipole moments, and no possibility of rotational, vibrational or electronic excitation in the dissociation process. The contrasting photodissociation dynamics associated with the different combinations of these solutes and solvents reported in this Dissertation both provides new understanding and raises questions concerning photoprocesses in partially solvated ionic complexes.
PB - University of Colorado Boulder PP - Boulder PY - 2012 TI - Photofragmentation and Recombination Dynamics of Partially Solvated Anionic Clusters ER -