Femtosecond mid-infrared photon echo study of an intramolecular hydrogen bond

The vibrational dephasing dynamics of O–H stretching excitations in a sterically well-defined intramolecular hydrogen bond (H bond) is studied by femtosecond photon echo spectroscopy in the mid-infrared. The O–H stretching vibration of phthalic acid monomethyl ester in inert solution displays a fast decay of phase coherence on a sub-100 fs time scale. Anharmonic coupling of the stretching motion to an underdamped low-frequency mode of the H bond gives rise to oscillations in the transient grating decay and the 3-pulse photon echo peak shift. Spectral diffusion dynamics on longer time scales is absent in such intramolecular H bonds, as opposed to the weaker intermolecular H bonds in water.