Nearly degenerate asymmetric stretches with perpendicular transition dipole moments of the deuterated guanidinium cation (DGdm(+)) in D2O and D-glycerol/D2O mixtures at 1600 cm(-1) were investigated by linear FTIR spectroscopy and polarization dependent femtosecond PUMP-probe spectroscopy. The vibrational coupling of the asymmetric stretches of guanidinium occurs within 0.5 ps and leads to fast decay of the anisotropy to a level of 0.1. A systematic study of the influence of the coherence transfer on pump-probe signals is given. Following this decay, the anisotropy decays with a time constant of 4.1 ps in D2O, by rotational diffusion about an axis perpendicular to the DGdm(+) mean plane. The presence of aggregation was demonstrated for concentrations higher than 0.2 M.