Driven Molecular Dynamics Studies of the Shared Proton Motion in the H5O2+·Ar Cluster: The Effect of Argon Tagging and Deuteration on Vibrational Spectra


Chemistry and Biochemistry

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We report IR spectra of H5O2(+) and H5O2(+)·Ar and their deuterium isotopologues using ab initio molecular dynamics. The trajectories were propagated as microcanonical (NVE) ensembles at energies corresponding to temperatures 50 and 100 K. The potential energy surface is calculated on-the-fly at the MP2/aug-cc-pVDZ level of theory. The calculations show that adding an argon atom to H5O2(+) introduces symmetry breaking in the Zundel core ion, causes blueshift in the shared proton vibration by about 200 cm(-1), and leads to the splitting of the OH stretch vibrations into four bands. Driven molecular dynamics (DMD) method is used to assign the spectrum by coupling the dipole moment to an external electric field oscillating at frequency ω. The broad feature at 1100 cm(-1) in the H5O2(+)·Ar spectrum is ascribed to the large amplitude shared proton vibration coupled with torsion and wag modes. MD MP2 simulations predict the H/D redshift in the shared proton vibration and water bending vibration to be about 280 and 460 cm(-1), respectively, in good agreement with experimental observations.