The effect of vibrational excitation and relaxation of the hydroxyl stretch on the hydrogen-bond structure and dynamics of stereoselectively synthesized syntetrol and anti-tetrol dissolved in deuterated chloroform are investigated via a mixed quantum-classical molecular dynamics simulation. Emphasis is placed on the changes in hydrogen-bond structure upon photoexcitation and the nonequilibrium hydrogen-bond dynamics that follows the subsequent relaxation from the excited to the ground vibrational state. The propensity to form hydrogen bonds is shown to increase upon photoexcitation of the hydroxyl stretch, thereby leading to corresponding absorption spectra. The vibrational excited state rule and the harmonic-Schofield quantum correction factor, and structure. The energy released during the relaxation from the involving the relaxing hydroxyl. The spectral signature of this a sizable red-shift of the infrared emission spectra relative to the lifetimes are calculated within the framework of Fermi's golden found to be sensitive reporters of the underlying hydrogen-bond excited to the ground state is shown to break hydrogen bonds nonequilibrium relaxation process is analyzed in detail.