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Identifying enantiomers in mixtures of chiral molecules with broadband microwave spectroscopy

MPS-Authors
/persons/resource/persons140390

Shubert,  V. Alvin
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, Notkestrasse 85, 22607 Hamburg, Germany;

/persons/resource/persons140388

Schmitz,  David
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, Notkestrasse 85, 22607 Hamburg, Germany;

/persons/resource/persons22077

Schnell,  Melanie
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, Notkestrasse 85, 22607 Hamburg, Germany;

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Citation

Shubert, V. A., Schmitz, D., Patterson, D., Doyle, J. M., & Schnell, M. (2014). Identifying enantiomers in mixtures of chiral molecules with broadband microwave spectroscopy. Angewandte Chemie International Edition, 53(4), 1152-1155. doi:10.1002/anie.201306271.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0024-BE65-7
Abstract
Chirality-sensitive broadband microwave spectroscopy was performed on mixtures of carvone enantiomers and conformers to distinguish enantiomers, measure enantiomeric excesses, and determine the absolute configurations of the enantiomers. This method uses microwave three-wave mixing and is inherently well-suited to the analysis of mixtures - a unique advantage over other techniques. In contrast to conventional microwave spectroscopy, the phase of the received signal is also exploited. This phase depends upon the signs of the molecules' dipole-moment components and is used to identify the excess enantiomer. The measured signal amplitude determines the size of the excess. The broadband capabilities of the spectrometer were used to simultaneously excite and measure two conformers of carvone, demonstrating the analysis of a sample with multiple chiral species. Employing quantum chemical calculations and the measured phases, the absolute configurations of the enantiomers are determined. Enantiomer differentiation, enantiomeric excess measurement, and absolute configuration determination within a mixture of gas-phase chiral molecules are demonstrated. In these experiments, microwave three-wave mixing within supersonic jets is combined with chirped-pulse broadband microwave spectroscopy. This new technique is now a significant step closer to broader application.