A joint community effort to critically evaluate quantum chemical approaches to the prediction of vibrational shifts of hydrates in the gas phase.

The first theory blind challenge addressing the effect of microsolvation on water vibrations is launched.

An organic radical monohydrate complex is detected in vacuum isolation at low temperature by FTIR supersonic jet spectroscopy for the first time. It is shown to exhibit a rich conformational and vibrational coupling dynamics, which can be drastically reduced by appropriate isotope substitution. Its detection with a new gas recycling infrared spectrometer demonstrates the thermal metastability of the gaseous TEMPO radical even under humid gas conditions. Compared to its almost isoelectronic and isostructural, closed shell ketone analogue, the hydrogen bond of the solvating water is found to be less directional, but stronger and more strongly downshifting the bonded water OH stretch vibration. A second solvent water directs the first one into a metastable hydrogen bond position to solvate the nitrogen center and the first water at the same time.

Fourier transform infrared (FTIR) absorption spectroscopy of cold molecules and clusters in supersonic slit jet expansions complements and extends more sensitive action spectroscopy techniques and provides important reference data for the latter. We describe how its major drawback, large substance and carrier gas consumption, can be alleviated by one to two orders of magnitude via direct and continuous recycling of the gas mixture. This is achieved by a combination of dry rotary lobe and screw pump compression. The signal-to-noise ratio is boosted by the established buffered giant gas pulse technique with full interferogram synchronization. The buildup of water impurities typically limits the recycling gain, but is turned into a feature for the study of hydrate complexes of volatile molecules. Continuous operation with a single gas filling over several days becomes practical and useful. Decadic absorbances in the low ppm range are detectable and the mid infrared range can be recorded simultaneously with the near infrared. The less straightforward hydration number assignment of spectral features in direct absorption spectroscopy is supported by a gradual water buildup at a rate of less than 0.5 mg/h. A recent reassignment proposal for the water dimer OH stretching spectrum is refuted and vibrational spectra of vacuum-isolated ${}^{18}$O-water clusters are presented for the first time. Methanol docking on asymmetric ketones is used to illustrate the advantages and limitations of the recycling concept. Previous assignments of the hydrate complex of 1-phenylethanol are confirmed. Additional features of the setup await testing and refinement, but the recycling technique already substantially widens the applicability of direct absorption spectroscopy of neutral molecular clusters. It may be attractive for other high-throughput jet spectrometers.

Tertiary amines are strong hydrogen bond acceptors. When a water molecule donates one of the OH groups, its in-phase stretching vibration wavenumber is decreased to such an extent that it comes close to the water bending overtone. This gives rise to anharmonic phenomena such as classical Fermi resonance, resonance with multiple-quantum dark states, or combination transitions with low-frequency intermolecular modes. These effects, which contribute to the spectral breadth of room-temperature hydrogen-bonded amine complexes, are disentangled by Fourier transform infrared spectroscopy in pulsed supersonic slit jet expansions. Monohydrates of the amines quinuclidine, N-methylpyrrolidine, N-methylpiperidine, and dimethylcyclohexylamine exhibit systematic mode coupling signatures. These suggest relatively fast energy flow out of the excited OH stretching fundamental into intra- and intermolecular degrees of freedom of the hydrogen-bonded water molecule. Trimeric complexes are spectroscopically separated from the amine monohydrates.