Mode-selective O-H stretching relaxation in a hydrogen bond studied by ultrafast vibrational spectroscopy.

The ultrafast relaxation of the excited O-H stretching vibration is studied by ultrafast infrared-pump/infrared-probe and infrared-pump/Raman-probe spectroscopy. We demonstrate a 200 fs lifetime of the hydrogen-bonded O-H stretching mode in 2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole (TINUVIN P). O-H stretching relaxation occurs through a few major channels that all involve combination and overtone bands of modes with considerable in-plane O-H bending character. In particular, the mode, which contains the largest O-H bending contribution, plays a prominent role for primary processes of intramolecular vibrational energy redistribution. Theoretical calculations of vibrational energy transfer rates based on a Fermi golden rule approach account for the experimental findings.