Hydrogen Bond Dynamics Probed with Ultrafast Infrared Heterodyne-Detected Multidimensional Vibrational Stimulated Echoes

Hydrogen bond dynamics are explicated with exceptional detail using multidimensional infrared vibrational echo correlation spectroscopy with full phase information. Probing the hydroxyl stretch of methanol-OD oligomers in ${\mathrm{C}\mathrm{C}\mathrm{l}}_4$, the dynamics of the evolving hydrogen bonded network are measured with ultrashort ($<50\mathrm{f}\mathrm{s}$) pulses. The data along with detailed model calculations demonstrate that vibrational relaxation leads to selective hydrogen bond breaking on the red side of the spectrum (strongest hydrogen bonds) and the production of singly hydrogen bonded photoproducts.