Anharmonic effects are especially important in the vibrational spectra of protonated water clusters. In this work we use the vibrational self-consistent field (VSCF) method and vibrational second-order perturbation theory (VPT2) methods to calculate the vibrational spectra of H+(H2O)n clusters with n from 1 to 21. Comparison is made with the experimental spectra obtained by vibrational predissociation of an H2 “tag” molecule. We also use calculations on subclusters and analysis of how the charge distributions change as the cluster is built up to identify the origins of the large anharmonic red shifts of the H3O+ vibrations in the larger clusters.

Anharmonic effects in vibrational spectra of protonated water clusters

249th National Meeting (2015)

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