Hydrogen sharing between two nitroxyl radicals in the gas phase and other microsolvation effects on the infrared spectrum of a bulky hydroxylamine.

The sterically hindered nitroxyl radical TEMPO is co-expanded with its hydroxylamine TEMPO-H in a supersonic jet and probed by FTIR spectroscopy. One major and one minor conformation of the 1 : 1 complex are identified by their OH stretching signatures, the major one exhibiting a weaker hydrogen bond. The acidic hydrogen atom in these structures can switch between the two TEMPO units in a more or less symmetric double minimum potential with a high barrier. Both conformations are experimentally shown to have a self-exchange quantum tunnelling period longer than 15 ps or 1500 OH vibrational periods even when excited by 41 kJ mol-1 along the OH stretching coordinate. The homodimer and more tentatively the monohydrate of TEMPO-H are also identified in the spectrum.

The first HyDRA challenge for computational vibrational spectroscopy.

Vibrational spectroscopy in supersonic jet expansions is a powerful tool to assess molecular aggregates in close to ideal conditions for the benchmarking of quantum chemical approaches. The low temperatures achieved as well as the absence of environment effects allow for a direct comparison between computed and experimental spectra. This provides potential benchmarking data which can be revisited to hone different computational techniques, and it allows for the critical analysis of procedures under the setting of a blind challenge. In the latter case, the final result is unknown to modellers, providing an unbiased testing opportunity for quantum chemical models. In this work, we present the spectroscopic and computational results for the first HyDRA blind challenge. The latter deals with the prediction of water donor stretching vibrations in monohydrates of organic molecules. This edition features a test set of 10 systems. Experimental water donor OH vibrational wavenumbers for the vacuum-isolated monohydrates of formaldehyde, tetrahydrofuran, pyridine, tetrahydrothiophene, trifluoroethanol, methyl lactate, dimethylimidazolidinone, cyclooctanone, trifluoroacetophenone and 1-phenylcyclohexane-cis-1,2-diol are provided. The results of the challenge show promising predictive properties in both purely quantum mechanical approaches as well as regression and other machine learning strategies.

Setting up the HyDRA blind challenge for the microhydration of organic molecules.

The procedure leading to the first HyDRA blind challenge for the prediction of water donor stretching vibrations in monohydrates of organic molecules is described. A training set of 10 monohydrates with experimentally known and published water donor vibrations is presented and a test set of 10 monohydrates with unknown or unpublished water donor vibrational wavenumbers is described together with relevant background literature. The rules for data submissions from computational chemistry groups are outlined and the planned publication procedure after the end of the blind challenge is discussed.

The Hydrates of TEMPO: Water Vibrations Reveal Radical Microsolvation.

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.

Pinacolone-Alcohol Gas-Phase Solvation Balances as Experimental Dispersion Benchmarks.

The influence of distant London dispersion forces on the docking preference of alcohols of different size between the two lone electron pairs of the carbonyl group in pinacolone was explored by infrared spectroscopy of the OH stretching fundamental in supersonic jet expansions of 1:1 solvate complexes. Experimentally, no pronounced tendency of the alcohol to switch from the methyl to the bulkier tert-butyl side with increasing size was found. In all cases, methyl docking dominates by at least a factor of two, whereas DFT-optimized structures suggest a very close balance for the larger alcohols, once corrected by CCSD(T) relative electronic energies. Together with inconsistencies when switching from a C4 to a C5 alcohol, this points at deficiencies of the investigated B3LYP and in particular TPSS functionals even after dispersion correction, which cannot be blamed on zero point energy effects. The search for density functionals which describe the harmonic frequency shift, the structural change and the energy difference between the docking isomers of larger alcohols to unsymmetric ketones in a satisfactory way is open.

Microhydration of Tertiary Amines: Robust Resonances in Red-Shifted Water.

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.

A Rather Universal Vibrational Resonance in 1:1 Hydrates of Carbonyl Compounds.

When the lower frequency OH stretching fundamental of a water molecule is shifted to the 3500 cm-1 spectral range by the solvation of a carbonyl compound, in this case a ketone, its infrared intensity is shared with a dark state. It is shown by chemical and isotope substitution for more than a dozen systems that the location of this resonance is remarkably substitution-independent. Harmonic and anharmonic model calculations support its assignment to a combination of the water bending overtone and in-plane water libration. This previously unrecognized intramolecular-intermolecular coupling in single solvent water has a strength of 7-10 cm-1. It may have been sporadically observed before in a few other carbonyl compounds such as amides, without any previous exploration of its potential universality. The resulting generic picosecond energy redistribution channel for aqueous solutions may represent a slow counterpart and doorway model of what happens on a subpicosecond time scale when the hydrogen bonds become stronger, such as in carboxylic acid dimers or protonated water clusters.