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Chiral Discrimination by Vibrational Spectroscopy Utilizing Local Modes
Author(s) -
Kraka Elfi,
Freindorf Marek,
Cremer Dieter
Publication year - 2013
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22130
Subject(s) - chemistry , glycidol , density functional theory , chirality (physics) , computational chemistry , spectroscopy , infrared spectroscopy , intermolecular force , photochemistry , molecule , organic chemistry , catalysis , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
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. Chirality 25:185–196, 2013 . © 2013 Wiley Periodicals, Inc.