Disentangling the Complex Vibrational Mechanics of the Protonated Water Trimer by Rational Control of Its Hydrogen Bonds

The vibrational spectrum of the protonated water trimer, H⁺(H₂O)₃, is surprisingly complex, with many strong features in the expected region of the fundamentals associated with two H-bonded OH groups on the H₃O⁺ core ion. Here we follow how the bands in this region of the spectrum evolve when the energies of the fundamentals in the H-bonded OH stretches are systematically increased by the attachment of increasingly strongly bound "tag" molecules (He, Ar, D₂, N₂, CO, and H₂O) to the free OH position on the hydronium core ion of H⁺(H₂O)₃, as well as by replacement of the hydrogen atom in the nonbonded OH group on hydronium with methyl and ethyl groups. This allows for the incremental transformation of the complex band pattern observed in H⁺(H₂O)₃ into that of the "Eigen" structure of the protonated water tetramer. Differences among the trajectories of the various bands provide an empirical way to disentangle features primarily due to the displacements of the OH stretches bound to the hydronium core from those arising from anharmonic coupling to states involving one or more quanta in lower frequency modes. The latter are found to be dramatically enhanced when the nominal frequencies of the intermolecular OH stretching modes approach those of the intramolecular bends of the H₃O⁺ and H₂O constituents in both H and D isotopologues.