Spectroscopy of substituted benzene molecules and metal rare gas interactions

• Main Author: Gardner, Adrian Michael
• Published: University of Nottingham 2013
• Subjects: 547.611
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.606296

The consistency of the labelling and assignments of the vibrations of the monosubstituted benzenes in the ground electronic state are investigated in this thesis. In doing so, many inconsistencies are uncovered, the origin of which is determined to be a result of the inherent problems in the previously employed assignment schemes. As a consequence, a new assignment scheme based on the vibrations of tluorobenzene is proposed. The SI electronic states of toluene and a -trideuterated toluene (toluene-d3) are investigated using resonance enhanced multi photon ionization, REMPI, spectroscopy. Using many of the observed SI vibrational levels as intermediates, two-colour, zero kinetic energy (ZEKE) spectroscopy has been employed in order to investigate the cationic ground states of these two toluene isotopologues. The vibrations are assigned using the nomenclature proposed in this thesis, and the activity of the vibrations in the REMPI and ZEKE spectra are discussed. Using high level ab initio techniques, potential energy curves, PECs, are calculated for the metal cation/rare gas, M+-RG (M = B, AI, Ga, and In) complexes. From these, spectroscopic parameters are derived, which are compared to previously reported experimental and theoretical values. The interactions between the moieties are examined by analyzing the orbital wavefunctions. The trends in the spectroscopic parameters determined for these complexes are compared with those previously determined for the RG complexes of the alkali metal, and the alkaline earth metal cations. Finally, the PECs of the ground electronic states of the coinage metal/rare gas complexes are calculated using high level ab initio techniques, with the interactions which occur within these complexes investigated