By a combination of linear FTIR and Raman jet spectroscopy, racemic trans-1,2-cyclohexanediol is shown to form an energetically unrivalled S₄-symmetric heterochiral dimer in close analogy to 1,2-ethanediol. Analogous experiments with enantiopure trans-1,2-cyclohexanediol reveal the spectral signature of at least three unsymmetric homochiral dimers. A comparison to signal-enhanced spectra of 1,2-ethanediol and to calculations uncovers at least three transiently homochiral dimer contributions as well. In few of these dimer structures, the intramolecular OH⋯O contact present in monomeric 1,2-diols survives, despite the kinetic control in supersonic jet expansions. This provides further insights into the dimerisation mechanism of conformationally semi-flexible molecules in supersonic jets. Racemisation upon dimerisation is shown to be largely quenched under jet cooling conditions, whereas it should be strongly energy-driven at higher temperatures. The pronounced energetic preference for heterochiral aggregation of vicinal diols is also discussed in the context of chirality-induced spin selectivity.

A multi-methodological investigation on the transiently chiral benzyl alcohol reveals a consistent preference for homochiral aggregation from the dimer to the tetramer.

A combination of linear infrared and Raman spectroscopy in supersonic slit jet expansions is used to clarify the conformational preferences in the dimer of the transiently chiral benzyl alcohol (phenylmethanol) under vacuum isolation. By experimentally exploring close analogies with the permanently chiral 1-phenylethanol, which is conformationally locked in the jet through intramolecular chirality induction, and by computational analysis of their conformational energy landscapes, several conclusions are drawn. The lowest energy dimer is confirmed to be cooperatively OH⋯OH⋯π-bonded and shown to be homochiral. Its heterochiral counterpart is slightly higher in energy and can be spectrally assigned as a minor constituent. A metastable heterochiral OH⋯π/OH⋯π structure with weakly coupled hydrogen bonds is efficiently trapped behind a C_i symmetry-enhanced barrier and can be assigned by IR/Raman mutual exclusion. Its homochiral counterpart is kinetically less stable but might be addressed by rotational spectroscopy. Ratings of standard density functionals with a standard basis set in terms of reproducing these experimental chirality synchronization benchmarks are presented.

A model is presented for the prediction of OH stretching fundamental wavenumbers of alcohol conformers in the gas phase by application of a small set of empirical anharmonicity corrections to calculations in the harmonic approximation. In contrast to the popular application of a uniform scaling factor, the local chemical structure of the alcohol is taken into account to greatly improve accuracy. Interestingly, different correction patterns emerge for results of hybrid density functional (B3LYP-D3 and PBE0-D3) and wave-function-based methods (SCS-LMP2, LCCSD(T*)-F12a and CCSD(T)-F12a 1D). This raises questions about electronic structure deficiencies in these methods and differences in anharmonicity between alcohols. After its initial construction on the basis of literature assignments the model is tested with Raman jet spectroscopy of propargyl alcohol, cyclohexanol, borneol, isopinocampheol and 2-methylbutan-2-ol. For propargyl alcohol a spectral splitting attributed to tunneling is resolved. PBE0-D3 is identified as a well performing and broadly affordable electronic structure method for this model. A mean absolute error of 1.3 cm⁻¹ and a maximum absolute error of 3 cm⁻¹ result for 46 conformers of 24 alcohols in a 60 cm⁻¹ range, when a single parameter is adjusted separately for each alcohol substitution class (methanol, primary, secondary, tertiary).