| Description |
Employment of Free Electron Lasers (FELs) and a Guided Ion Beam Tandem Mass Spectrometer (GIBMS) has allowed for the spectroscopic and spectrometric investigations of a variety of ionic complexes, respectively. The data presented in Chapters 2 and 3 of this thesis were obtained using two FELs located at the Free Electron Lasers for Infrared eXperiments (FELIX) Laboratory at Radboud University in Nijmegen, The Netherlands. Specifically, Chapter 2 presents an evaluation of the activation of deuterated methane by 5d transition metal cations (Pt+, Ir+, Ta+, and W+) via infrared multiphoton dissociation (IRMPD) spectroscopy and density functional theoretical methodologies. For this study, the Free Electron Laser of IntraCavity Experiments (FELICE) was employed to ascertain the experimental IRMPD spectra. Theory was completed at the B3LYP/def2-TZVPPD level and basis set for all systems. More so, this study was the first of its kind to employ rotational contours in conjunction with IRMPD spectra. Rotational contours were also explored to assess the non-negligible rotational broadening observed in these systems. These rotational contours were included in this study due to the rotational constants of these ionic complexes being of the same order as the spectral bandwidth of FELICE. Spectroscopic determination of unexpected resonance bands in the infrared spectrum, previously observed in the perprotio system, are tentatively made and supported using these methods. Chapter 3 concerns the metal-dependent binding of lysine and deprotonated lysine to CdCl+ and Zn2+, respectively. This investigation was completed using a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR-MS) in tandem with the Free Electron Laser for Infrared eXperiments (FELIX). These experimental action spectra were then complemented by theoretical calculations that employed the B3LYP, B3LYP-GD3BJ, B3P86, and MP2 levels of theory using basis sets specific to Zn and Cd, due to the latter needing a small core effective core potential. The combination of the FT-ICR, FELIX, and ab initio calculations has been established as one of the most robust methodologies for making conformational determinations of metal-bound amino acids in the gas-phase. Chapters 4 and 5 of this thesis present data obtained using a guided ion beam tandem mass spectrometer (GIBMS) located in the Armentrout Research Group at the University of Utah. This instrumentation allows for the ascertainment of thermochemical data over a broad range of kinetic energies, and is regarded by the NIST webbook as the "most robust methodology for determining bond dissociation energies"[footnote reference] and other related thermochemical information for ionic, gas-phase species. Chapter 4 focuses on a thermochemical investigation into the BDE of the gold dimer cation (Au2+). This study employed well-established CID methodologies and was complemented with density functional theoretical calculations computed at the B3LYP, M06-2x, and CCSD(T,full) levels of theory. All theoretical calculations reported in this chapter employed the def2-TZVPPD basis set for Au. This study presents the first direct measurement for the BDE of Au2+, a value that is relevant to present-day studies probing the catalytic activity of Au2+, specifically with regard to the activation of methane. Chapter 5 of this thesis details a study regarding the reaction enthalpy of holmium in the ionospheric chemi-ionization reaction. This investigation concerns the observation of Ho+ in exchange reactions with CO, SO2, and O2, as well as CID of HoO+ by interactions with O2 and Xe. Extensive quantum chemical theoretical calculations are reported here, where the BDEs for HoC+ and HoO+ are obtained at the B3LYP, PBE0, MP2(full), and CCSD(T,full) levels of theory, each of which employs the Stuttgart Dresden (SDD), Atomic Natural Orbital (ANO), and Segmented SDD (Seg. SDD) basis set for Ho and the 6-311+G(3df,3pd) basis set for C and O. This study is still ongoing and is supplemented by a discussion regarding work that still needs to be completed following submission of this thesis. |
