Hydrogen bond population dynamics are extricated with exceptional detail using ultrafast (<50 fs) infrared multidimensional stimulated vibrational echo correlation spectroscopy with full phase information and frequency resolved infrared pump-probe experiments performed on the hydroxyl stretch of methanol-OD oligomers in CCl4. Hydrogen bond breaking makes it possible to acquire data for times much greater than the hydroxyl stretch vibrational lifetime. The correlation spectra and detailed calculations demonstrate that vibrational relaxation leads to hydrogen bond breaking for oligomers that have hydroxyl stretch frequencies on the low energy (red) side of the hydroxyl stretch spectrum, the spectral region that is associated with the strongest hydrogen bonds. Frequency resolved pump-probe data support the conclusions drawn from the correlation spectra. Using a global fit to the pump-probe spectra, in conjunction with assignments made possible through the correlation spectra, it is demonstrated that the residual ground state and photoproduct of hydrogen bond breaking are prepared near their thermal equilibrium distribution. The spectrum of the hydrogen bond breaking photoproduct and the residual ground state approach the steady-state temperature difference spectrum on the tens of picoseconds time scale, indicating the system thermalizes on this time scale. (C) 2003 American Institute of Physics.