While it is generally recognized that the hydroxide ion can rapidly diffuse through aqueous solution due to its ability to accept a proton from a neighboring water molecule, a description of the OH(-) solvation structur and mechanism of, proton transfer to the ion remains controversial. In this report, we present the results of femtosecond infrared spectroscopy measurements of the O-H stretching transition of dilute HOD dissolved in NaOD/D(2)O. Pump-probe, photon echo peak shift, and two-dimensional infrared spectroscopy experiments performed as a function of deuteroxide concentration are used to assign spectral signatures that arise from the OH. ion and its solvation shell. A spectral feature that decays on a similar to 110 fs time scale is assigned to the relaxation of transiently formed configurations wherein a proton is equally shared between a HOD molecule and an OD(-) ion. Over picosecond waiting times, features appear in 2D IR spectra that are indicative of the exchange of population between OH(-) ions and HOD molecules due to deuteron transfer. The construction of a spectral model that includes spectral relaxation, chemical exchange, and thermalization processes, and self-consistently treats all of our data, allows us qualitatively explain the results of our experiments and gives a lower bound of 3 ps for the deuteron transfer kinetics.