Beyond local group modes in vibrational sum frequency generation

The Journal of Physical Chemistry. a
Hilary M ChaseFranz M Geiger

Abstract

We combine deuterium labeling, density functional theory calculations, and experimental vibrational sum frequency generation spectroscopy into a form of "counterfactual-enabled molecular spectroscopy" for producing reliable vibrational mode assignments in situations where local group mode approximations are insufficient for spectral interpretation and vibrational mode assignments. We demonstrate the method using trans-β-isoprene epoxydiol (trans-β-IEPOX), a first-generation product of isoprene relevant to atmospheric aerosol formation, and one of its deuterium-labeled isotopologues at the vapor/silica interface. We use our method to determine that the SFG responses that we obtain from trans-β-IEPOX are almost exclusively due to nonlocal modes involving multiple C-H groups oscillating at the same frequency as one vibrational mode. We verify our assignments using deuterium labeling and use DFT calculations to predict SFG spectra of additional isotopologues that have not yet been synthesized. Finally, we use our new insight to provide a viable alternative to molecular orientation analysis methods that rely on local mode approximations in cases where the local mode approximation is not applicable.

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Citations

Apr 12, 2016·The Journal of Physical Chemistry. a·Mary Alice UpshurFranz M Geiger
Jun 17, 2016·The Journal of Chemical Physics·Daniel P TaborEdwin L Sibert
Jan 20, 2017·The Journal of Physical Chemistry. a·Hilary M ChaseFranz M Geiger
Apr 10, 2021·The Journal of Physical Chemistry. B·Michael von DomarosDouglas J Tobias

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