This work contains two main areas of research within the field of bonding and spectroscopy. The first is the interactions of metals and metal ions with rare gas atoms; the second concerns vibrational dynamics in para-fluorotoluene(pFT). The research has been carried out as part of a collaboration between the SOCAR and Reid groups at the University of Nottingham and also involved external research teams. The work combines the results from experiments employing several different spectroscopic techniques with theoretical calculations, which support the experimental data, assist in their interpretation and provide new information. Resonance enhanced multiphoton ionisation spectroscopy is employed to investigate the Au–Xe and Au–Ne neutral complexes in the region of the 62PJ ← 62S1/2 Au atomic transition. High-level ab initio calculations provide further insight, which is necessary to explain the unusual spectra obtained. A theoretical study of complexes containing Group 2 metal cations and rare gases also reveals some unexpected trends that are related to some of the effects seen in the Au–RG series. A combination of nanosecond zero electron kinetic energy spectroscopy and time-resolved picosecond photoelectron spectroscopy is employed to investigate the vibrational dynamics of pFT. Excitation via several different vibrational states allows the study of a Fermi resonance, statistical intramolecular vibrational energy redistribution and an intermediate case that shows evidence of so-called “doorway states”.