The recently developed efficient protocol to explicit quantum mechanical modeling of structure and IR spectra of liquids and solutions (S. A. Katsyuba, S. Spicher, T. P. Gerasimova, S. Grimme, J. Phys. Chem. B 2020, 124, 6664) is applied to ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium bromide (EmimBr), its C2‐deuterated analog [Emim‐d]Br and its aqueous solutions. It is shown that the solvation strongly modifies frequencies and IR intensities of the CH/CD stretching vibrations (νCH/νCD) of the imidazolium ring. The main vibrational spectroscopic features of the neat IL are reproduced by the simulations for a cluster (EmimBr)9, in which all three imidazolium CH moieties of the solvated cation form short contacts with three Br− anions, and another two Br− anions are located on top and bottom of imidazolium ring. Cluster models of aqueous solutions reproduce the experimental vibrational frequencies of actual solutions, provided that the Br− anion of solvated contact ion pair (CIP) is situated on top of imidazolium ring, and CH/CD moieties of the latter participate in short contacts with surrounding water molecules. Both structural and spectroscopic analysis allow to interpret the short contacts CH/CD⋯Br− and CH/CD⋯OH2 as hydrogen bonds of approximately equal strength. Enthalpies of bonding of these liquid‐state H‐bonds, estimated with the use of empirical correlations, amount to ca. 1.4 kcal⋅mol−1, while the analogous estimates obtained for the gas‐phase charged species [Emim]2Br+ increase to 5.6 kcal⋅mol−1. It is shown that formation of solvent‐shared ion pair (SIP) in aqueous solution, where the counterions of IL are separated by two water molecules H‐bonded to a Br− anion, produces frequency shifts ΔνCH/CD, strongly different from the case of CIP formation. This difference can be used for IR/Raman spectroscopic differentiation of the type of solvated ion pairs of EmimBr or other related ILs.
