American Chemical Society
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Accurate Calculations of OH-Stretching Intensities with a Reduced-Dimensional Local Mode Model Including Eckart Axis Embedding

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journal contribution
posted on 2020-01-24, 16:48 authored by Emil Vogt, Pablo Bertran Valls, Henrik G. Kjaergaard
Absolute OH- and OD-stretching transition intensities have been calculated for a series of alcohols (methanol, ethanol, 2-propanol, 1-propanol, and tert-butanol) with one-dimensional (1D) and three-dimensional (3D) local mode models. We compare the calculated intensities for the ΔvOH = 1–5 and ΔvOD = 1–3 transitions with experimental values. Potential energy and dipole moment surfaces are calculated at the CCSD­(T)-F12a/VDZ-F12 level of theory. The 1D local mode model includes only the OH­(D)-stretching mode, whereas the 3D local mode model also includes the CO-stretching and COH­(D)-bending modes. We analyze the effect on vibrational intensities of using either a molecule-fixed Eckart frame or a space-fixed Cartesian frame. We find that both Eckart embedding and inclusion of the CO-stretching and COH­(D)-bending modes in the local mode model are important for the OH/OD-stretching fundamental transition intensities, but have a minor effect on overtone intensities. The 3D reduced-dimensional local model, when combined with coupled cluster surfaces, accurately predicts OH/OD-stretching transition intensities and wavenumbers, for all alcohols included in this work.