Publication Details (including relevant citation information):
Garrett-Roe, S. and Hamm, P. J. Chem. Phys. 128, 104507 (2008).
Characterizing the dynamics of the OH stretch in isotopically substituted liquid water (HOD in D2 O) in terms of 3-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 3-point correlation functions are sensitive to this motion, unlike 2-point correlation functions, and can select sets of trajectories which linger in the area of the transition state. 3D-IR correlation spectroscopy could potentially measure these dynamics, though motional narrowing significantly changes the shape of the resulting spectra.
Address (URL): http://dx.doi.org/10.1063/1.2883660