title: Rotational spectroscopy and three-wave mixing of 4-carvomenthenol: A technical guide to measuring chirality in the microwave regime.
abstract: We apply chirality sensitive microwave three-wave mixing to 4-carvomenthenol, a molecule previously uncharacterized with rotational spectroscopy. We measure its rotational spectrum in the 2-8.5 GHz range and observe three molecular conformers. We describe our method in detail, from the initial step of spectral acquisition and assignment to the final step of determining absolute configuration and enantiomeric excess. Combining fitted rotational constants with dipole moment components derived from quantum chemical calculations, we identify candidate three-wave mixing cycles which were further tested using a double resonance method. Initial optimization of the three-wave mixing signal is done by varying the duration of the second excitation pulse. With known transition dipole matrix elements, absolute configuration can be directly determined from a single measurement.
authors.affiliation: Max Planck Institute for the Structure and Dynamics of Matter, 22761 Hamburg, Germany.
authors.forename: V Alvin
authors.initials: VA
authors.lastname: Shubert
authors.affiliation: Max Planck Institute for the Structure and Dynamics of Matter, 22761 Hamburg, Germany.
authors.forename: David
authors.initials: D
authors.lastname: Schmitz
authors.affiliation: Max Planck Institute for the Structure and Dynamics of Matter, 22761 Hamburg, Germany.
authors.forename: Chris
authors.initials: C
authors.lastname: Medcraft
authors.affiliation: Max Planck Institute for the Structure and Dynamics of Matter, 22761 Hamburg, Germany.
authors.forename: Anna
authors.initials: A
authors.lastname: Krin
authors.affiliation: Department of Physics, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: David
authors.initials: D
authors.lastname: Patterson
authors.affiliation: Department of Physics, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: John M
authors.initials: JM
authors.lastname: Doyle
authors.affiliation: Max Planck Institute for the Structure and Dynamics of Matter, 22761 Hamburg, Germany.
authors.forename: Melanie
authors.initials: M
authors.lastname: Schnell
mesh_terms: D008610:Menthol / Q000031:analogs & derivatives* / Q000737:chemistry; D008872:Microwaves; D011789:Quantum Theory; D012399:Rotation; D013057:Spectrum Analysis
chemical_list: C534301:4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol; D008610:Menthol