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Accuracy of quantum chemistry structures of chiral tag complexes and the assignment of absolute configuration

Kevin Mayer, Channing West, F. E. Marshall, Galen Sedo, G.S. Grubbs, Luca Evangelisti, Brooks H. Pate

2022Physical Chemistry Chemical Physics25 citationsDOIOpen Access PDF

Abstract

C isotopomer spectra of five of these species are assigned in natural abundance. Analysis of these spectra provides direct structural characterization of the complexes through determination of the carbon atom position coordinates. This data set is used to benchmark quantum chemistry calculations of candidate equilibrium geometries of the chiral tag complexes. The quantum chemistry calculations are limited to methods commonly used in the field of rotational spectroscopy. It is shown that the accuracy of the structures from quantum chemistry provides a high-confidence assignment of cluster geometries to the observed spectra. As a result, a high-confidence determination of the analyte (verbenone) absolute configuration is achieved.

Topics & Concepts

Absolute configurationMoleculeChemistryAnalyteQuantum chemistryComputational chemistrySpectral lineStereochemistryPhysical chemistryOrganic chemistryPhysicsSupramolecular chemistryQuantum mechanicsMolecular Spectroscopy and StructureMolecular spectroscopy and chiralityAnalytical Chemistry and Chromatography
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