Unmasking Rare, Large-Amplitude Motions in D2-Tagged I-·(H2O)2 Isotopomers with Two-Color, Infrared-Infrared Vibrational Predissociation Spectroscopy.

Abstract

We describe a two-color, isotopomer-selective infrared-infrared population-labeling method that can monitorvery slow spectral diffusion of OH oscillators in H-bondednetworks and apply it to the I-·(HDO)·(D2O) and I-·(H2O)·(D2O) systems, which are cryogenically cooled and D2-tagged at an ion trap temperature of 15 K. These measurements reveal very large (>400 cm-1), spontaneous spectral shifts despite the fact that the predissociation spectra in the OH stretching region of both isotopologues are sharp and readily assigned to four fundamentals of largely decoupled OH oscillators held in a cyclic H-bonded network. This spectral diffusion is not observed in the untagged isotopologues of the dihydrate clusters that are generated under the same source conditions but does become apparent at about 75K. These results are discussed in the context of the large-amplitude "jump" mechanism for H-bond relaxation dynamics advanced by Laage and Hynes in an experimental scenario where rare events can be captured by following the migration of OH groups among the four available positions in the quasi-rigid equilibrium structure.