title: 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.
authors.affiliation: Physikalish-Chemisches Institut, Universität Zürich, Winterthurerstr 190, Zürich, Switzerland.
authors.forename: Sean
authors.initials: S
authors.lastname: Garrett-Roe
authors.forename: Peter
authors.initials: P
authors.lastname: Hamm