title: Chiral discrimination by vibrational spectroscopy utilizing local modes.
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.
authors: Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University, 3215 Daniel Ave., Dallas, TX 75275-03114, USA. ekraka@smu.edu
authors: Elfi
authors: E
authors: Kraka
authors: Marek
authors: M
authors: Freindorf
authors: Dieter
authors: D
authors: Cremer