We present a first-principles simulation study of vibrational spectral diffusion and hydrogen-bond dynamics in solution of a fluoride ion in deuterated water. The present calculations are based on abinitio molecular dynamics simulation for trajectory generation and wavelet analysis for calculations of frequency fluctuations. The O-D bonds of deuterated water in the anion hydration shell are found to have lower stretching frequency than the bulk water. The dynamical calculations of vibrational spectral diffusion for hydration shell water molecules reveal three time scales: a short-time relaxation (~100 fs) corresponding to the dynamics of intact ion-water hydrogen bonds, a slower relaxation (~7.5 ps) corresponding to the lifetimes of fluoride ion-water hydrogen bonds, and an even longer time scale (~26 ps) associated with the escape dynamics of water from the anion hydration shell. However, the slowest time scale is not observed when the vibrational spectral diffusion is calculated over O-D bonds of all water molecules, including those in the bulk. © 2012 IUPAC.