Spectroscopic
studies of protonated water clusters (PWCs) have
yielded enormous insights into the fundamental nature of the hydrated
proton. Here, we introduce a new coupled local-mode (CLM) approach
to calculate PWC OH stretch vibrational spectra. The CLM method combines
a sampling of representative configurations from density functional
theory (DFT)-based ab initio molecular dynamics (AIMD)
simulations with DFT calculations of local-mode vibrational frequencies
and couplings. Calculations of inhomogeneous OH stretch vibrational
spectra for H+(H2O)4 and H+(H2O)21 agree well with experiment and higher-level
calculations, and decompositions of the calculated spectra in terms
of the coupled modes aids in the interpretation of the spectra. This
observation is consistent with the idea that capturing anharmonicity
and coupling is as important to accuracy as the underlying level of
electronic structure theory. The CLM calculations can easily discern
the configuration that dominates the experimental measurement for
H+(H2O)5, which can adopt several
low-energy conformations.
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