Using the resonant two-photon ionization (R2PI) and mass analyzed threshold ionization (MATI) spectroscopic techniques, we have recorded the vibrationally resolved spectra of p-bromoaniline in the S1 and cationic ground state. The band origin of the S1

One-color resonance two-photo ionization (R2PI) spectra of mixed clusters of styrene molecule (S) with polar molecules [water (W), methanol (M), ethanol (E), and trifuoroethanol (T)] were measured through the S1←S0 transition of the styrene molecule. The spectra reveal a rapid increase in complexity with the number of polar molecules in the cluster, associated with van der Waal modes and isomeric forms. The spectral shifts of the cluster origins from the S1-S0 transition of the bare styrene molecule reflect the nature of the intermolecular interactions within the binary clusters. The obtained R2PI spectra xv were compared with the spectra of the analogous benzene containing clusters. The styrene-water and the styrene-methanol complexes exhibited very different spectral shifts and structures as compared to the benzene-water and benzene-methanol complexes, respectively. The favorable interactions of polar molecules with the olefin group of styrene may explain the strong inhibition effects of exerted by small concentrations of water and alcohols on the cationic polymerization of styrene. Size-specified intracluster proton transfer reactions were observed for mixed clusters of styrene dimer with water, methanol and ethanol molecules. It was proposed that the polar molecules tend to aggregate around the olefin center, which promotes the transfer of the charge from the propagating chain to the hydrogen-bonded polar molecules subcluster. The minimum number of polar molecules required for a proton transfer to take place exothermically depends on the proton affinity of the polar molecules subcluster. The estimated upper limit value for the proton affinity of styrene dimer radical was evaluated based on the energetic of the proton transfer reaction to be ≤ 220.4 kcal/mol. No intracluster reaction was observed for styrene-trifluoroethanol (STn) system. In order to provide a comparison between the styrene and benzene systems, the benzene-ethanol (BEn) and benzene-trifluoroethanol (BTn) clusters were studied by using the R2PI technique via the 6¹0 transition of the benzene molecule. Both dissociative electron transfer and dissociative proton transfer reactions were observed within the BEn clusters, where n = 2 and 3, respectively. Proton transfer reactions were observed following dissociative electron transfer reactions within the (BTn) clusters, where n = 4, to generate the protonated clusters (H+Tn).

Metal-cyclic hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and IR-UV resonant two-photon ionization (R2PI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the ZEKE measurements with density functional theory (DFT) calculations. In addition, C-H stretching frequencies were measured from the R2PI spectra. In this dissertation, metal complexes of 1, 3, 5, 7-cyclo-octatetraene (COT), toluene, p-xylene, mesitylene, hexamethylbenzene, biphenyl, naphthalene, pyrene, perylene, and coronene were studied. For each metal-ligand complex, different effects from the metal coordination have been identified. Although free COT is a nonaromatic molecule with a tub-shaped structure, the group III transition metal atoms (Sc, Y, and La) donate two electrons to a partially filled π orbital of COT, making the ligand a dianion. As a result, metal coordination converts COT into a planar, aromatic structure and the resulting complex exhibits a half-sandwich structure. For the Sc(methylbenzene) complexes, the benzene rings of the ligands are bent and the π electrons are localized in a 1, 4-diene fashion due to differential Sc binding with the carbon atoms of the rings. Due to differential metal binding, the degenerate d orbitals split and the Sc-methylbenzene complexes prefer the low-spin ground electronic states. In addition, as the number of methyl group substituents in the ligand increases, the ionization energies (IEs) of the Sc-methylbenzene complexes decrease. However, Ti, V, or Co coordination does not disrupt the delocalized π electron network within the carbon skeleton in the high-spin ground states of the metal complexes. For group VI metal (Cr, Mo, and W)-bis(toluene) complexes, methyl substitution on the benzene ring yields complexes with four rotational conformers of 0°, 60°, 120°, and 180° conformation angles between two methyl groups. In addition, variable-temperature ZEKE spectroscopy using He, Ar, or their mixtures has determined the totally eclipsed 0° rotamer to be the most stable. When there are two equivalent benzene rings, the metal (Ti, Zr or Hf) binds to both the benzene rings of biphenyl, or the metal (Li) binds to one of the benzene rings of naphthalene. On the other hand, the metal (Li) favors the ring-over binding site of the benzene ring with a higher π electron content and aromaticity in pyrene, perylene, and coronene.