Three-point frequency fluctuation correlation functions of the OH stretch in liquid water

Abstract

Characterizing the dynamics of the OH stretch in isotopically substituted liquid water (HOD in D(2)O) in terms of three-point frequency fluctuation correlation functions and joint probability densities shows that dynamics during hydrogen bond rearrangements occur primarily along a coordinate which is perpendicular to the spectroscopic coordinate. Molecular dynamics simulations show that three-point correlation functions are sensitive to this motion, unlike two-point correlation functions, and can select sets of trajectories which linger in the area of the transition state. Three-dimensional-infrared correlation spectroscopy could potentially measure these dynamics, though motional narrowing significantly changes the shape of the resulting spectra.