The ionization of liquid water produces three primary reactive radical species; the solvated electron (e-aq), the hydroxyl radical (Ì¢ âÂå¢OH) and the hydrogen atom (HÌ¢ âÂå¢) each capable of reacting with an organic substrate to form a radical adduct. This dissertation presents a detailed investigation of the spectroscopic and kinetic properties for a number of such short-lived radical adducts. The model system chosen for this work was benzoate, enabling the additional inquiry into the role of protonation on the kinetics and molecular structure of the various transients formed. Hydroxyl radical oxidation of aromatics in aqueous solution produces hydroxycyclohexadienyl radicals as intermediates. To date there has been little understanding of the vibrational spectra, structure and electronic absorption of these transients in water. These radicals are characterized by the presence of a relatively strong transient absorption in the near-UV. Identification of the molecular structure and kinetic parameters of the species contributing to this absorption requires a structural technique linked to absorption. We have applied time-resolved resonance Raman (TR-RR) spectroscopy to structurally identify isomers of cyclohexadienyl radicals formed in pulse radiolysis, using aqueous benzoate solutions as a model system. An early electron spin resonance (ESR) study [Eiben, et al.; J. Phys. Chem. 1971, 75, 1186.] has shown that a mixture of three benzoate hydroxycyclohexadienyl radical isomers: ortho-, meta- and para- are formed upon electron irradiation of N2O saturated benzoate solution. Their collective transient absorption is observed to exhibit a single broad band in the near UV region (Ì_åÈmax = 330 nm, Ì_åµ330 = 3400 M-1cm-1). Extracting the single isomeric contribution to this collective absorption requires probing the TR RR spectra at individual wavelengths within the broad transient absorption range looking for a characteristic indication of each individual isomer. Raman signals of various para substituted benzoates were also collected to aid in the vibrational studies of the aforementioned benzoate hydroxycyclohexadienyl radicals. Ionizing radiation can be used to selectively induce redox reactions that are found in naturally occurring systems. This dissertation also explores the reaction between the hydrated electron and benzoate by absorption and TR-RR spectroscopy. Initially this reaction forms the benzoate radical dianion, absorbing at ~320 nm and 440 nm, which depending on the pH will react with water on a 10 ns time scale forming the protonated radical monoanion whose absorption is blue shifted by 10 nm in both bands. Both the transient absorption and resonance Raman spectra excited at 341 nm are similar for these radical anions indicating prontonation has minimal effect on the nuclear and electronic structure. However, the observed resonance Raman enhancement of these radicals was weaker than transients with similar extinction coefficients. Electron photodetachment was concluded to be responsible for this observation as it is a very fast photochemical process that can compete with Raman scattering. The details of the various findings from vibrational spectroscopy will be discussed in this dissertation.