| This dissertation is aimed at a clear representation of a series of experiments that outline a general method for the separation of the components of an infrared vibrational spectrum. In the first experiment, differential electron detachment energy is used to separate out the OH stretching vibrational spectrum of the type I isomer of the water hexamer anion from that of the lower-binding type II. What follows is a set of experiments laying out the procedure for a new, generalized, isomer-selective spectroscopy method involving three stages of mass selection and two laser interactions in an argon-mediated time-of-flight mass spectrometric regime. This method is used in three different modes. The first peels apart and isolates the individual infrared spectra of the NO-2˙H2O ion-water pair into two isomer-specific vibrational spectra. The second investigates the interconversion energies of the two isomers found in the previous study, finding that the isomers are able to convert in one direction with injection of ∼1203 cm-1, while the other will convert with injection of ∼3000 cm-1. The third mode involves incorporation of a single D2O molecule into the water hexamer anion to form D2OH2O -6 , where the D2O is used as an embedded reporter that reads out its unique position within the water network. In this study the transitions in the OD stretch region assigned to the so-called AA water molecule are shown to arise from the same position of the D2O as that in the DOD bend region. |
