Hydration Rearrangement in the 4‐Aminobenzonitrile−(H2O)2 Cluster Induced by Photoionization: The Effect of Solvent‐Solvent Interactions

Abstract

AbstractThe interplay between solute‐solvent and solvent‐solvent interactions plays an essential role in solvation dynamics that has important effects on the mechanism and dynamics of chemical reactions in solution. In this study, the rearrangement of the hydration shell induced by photoionization of a solute molecule is probed in a state‐ and isomer‐specific manner by resonant multiphoton ionization detected IR spectroscopy of the prototypical 4‐aminobenzonitrile−(H2O)2 cluster produced in a molecular beam. IR spectra reveal that the water molecules form a cyclic solvent network around the CN group in the initial neutral state (S0). Different from the singly‐hydrated cluster, in which either the CN or the NH2 group is hydrated, hydration of the NH2 group is not observed in the dihydrated cluster. IR spectra obtained after ionizing the solute molecule into the cation ground state (D0) exhibit features ascribed to both NH‐bound and CN‐bound isomers, indicating that water molecules migrate from the CN to the NH site upon ionization with a yield depending on the ionization excess energy. Analysis of the IR spectra as a function of the excess energy shows that migration produces two different NH2 solvated structures, namely (i) the most stable structure in which both N−H bonds are singly hydrated and (ii) the second most stable isomer in which one of the N−H bonds is hydrated by a H‐bonded (H2O)2 dimer. The product branching ratio of the two isomers depends on the excess energy. The role of the water‐water interaction in the hydration rearrangement is discussed based on the potential energy landscape. Solvation dynamics plays an important role in reaction mechanisms in the condensed phase, where not only solute‐solvent solvation but also solvent‐solvent interactions have a significant influence on the dynamics. Thus, the investigation of solvation dynamics at the molecular level substantially contributes to our understanding of the reaction mechanism. In this study, the dihydrated cluster of 4ABN was utilized as a model for the first solvation layer to elucidate solvent motions induced by ionization of the solute and the role of W−W interactions for the solvent relaxation.