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Updated: May 15, 2026

Multimodal Nonlinear Hyperspectral Chemical Imaging Using Line-Scanning Vibrational Sum-Frequency Generation Microscopy
Published on: December 1, 2023
Chiral discrimination by vibrational spectroscopy utilizing local modes
Elfi Kraka1, Marek Freindorf, Dieter Cremer
1Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University, 3215 Daniel Ave., Dallas, TX 75275-03114, USA. ekraka@smu.edu
Abstract:
Chiral discrimination of homochiral and heterochiral H-bonded complexes is a challenge for both experimentalists and computational chemists. It is demonstrated that a two-pronged approach based on far-infrared vibrational spectroscopy and the calculation of local mode frequencies facilitates the chiral discrimination of H-bonded dimers. The local H-bond stretching frequencies identify the strongest H-bonds and by this the dominating chiral diastereomer. This is shown in the case of peroxide, trioxide, hydrazine, glycidol, and butan-2-ol dimers as well as propylene oxide···glycidol complexes investigated with the help of second-order Møller-Plesset perturbation, coupled cluster, and density functional theory calculations where, in the latter case, the ωB97X-D functional was used for an improved description of H-bonding. In some cases, additional intermolecular interactions overrule the important role of H-bonding, which is found by calculating chirodiastaltic energies.
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