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

We describe a two-color, isotopomer-selective infrared–infrared population-labeling method that can monitor very slow spectral diffusion of OH oscillators in H‑bonded networks 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 75 K. 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

Disentangling the Complex Vibrational Spectrum of the Protonated Water Trimer, H⁺(H₂O)₃, with Two-Color IR-IR Photodissociation of the Bare Ion and Anharmonic VSCF/VCI Theory

Vibrational spectroscopy of the protonated water trimer provides a stringent constraint on the details of the potential energy surface (PES) and vibrational dynamics governing excess proton motion far from equilibrium. Here we report the linear spectrum of the cold, bare H⁺(H₂O)₃ ion using a two-color, IR-IR photofragmentation technique and follow the evolution of the bands with increasing ion trap temperature. The key low-energy features are insensitive to both D₂ tagging and internal energy. The D₂-tagged D⁺(D₂O)₃ spectrum is reported for the first time, and the isotope dependence of the band pattern is surprisingly complex. These spectra are reproduced by large-scale vibrational configuration interaction calculations based on a new full-dimensional PES, which treat the anharmonic effects arising from large amplitude motion. The results indicate such extensive mode mixing in both isotopologues that one should be cautious about assigning even the strongest features to particular motions, especially for the absorptions that occur close to the intramolecular bending mode of the water molecule