Model of Hydrogen-Bond Interactions Near the Equilibrium Configuration. Application to Vibrational Energy Transfer in DF(V=N) + DF(V=0) 1a.

摘要

A model is developed in order to study near-equilibrium behavior of hydrogen-bond systems, in which individual molecules are considered to undergo hindered rotational motion and back-and-forth translational motion. The hindered rotational motion is described quantum mechanically, while the translational motion is analyzed in classical dynamics. Application of the model is made to calculate energy transfer probabilities of DF(v=n) + DF(v=0) goes to DF(v=n -1) + DF(v+1) for n = 2-5 at low temperatures, where the energy mismatch is transferred to the back-and-forth translational motion. As temperature increases, the formation of hydrogen bonds becomes less important, and energy transfer probabilities decrease sharply.