Structural and Electronic Evolution of Ethanolamine upon Microhydration: Insights from Hyperfine Resolved Rotational Spectroscopy.

Ethanolamine hydrates containing from one to seven water molecules were identified via rotational spectroscopy with the aid of accurate quantum chemical methods considering anharmonic vibrational corrections. Ethanolamine undergoes significant conformational changes upon hydration to form energetically favorable hydrogen bond networks. The final structures strongly resemble the pure (H2O)3-9 complexes reported before when replacing two water molecules by ethanolamine. The 14N nuclear quadrupole coupling constants of all the ethanolamine hydrates have been determined and show a remarkable correlation with the strength of hydrogen bonds involving the amino group. After addition of the seventh water molecule, both hydrogen atoms of the amino group actively contribute to hydrogen bond formation, reinforcing the network and introducing approximately 21-27 % ionicity towards the formation of protonated amine. These findings highlight the critical role of microhydration in altering the electronic environment of ethanolamine, enhancing our understanding of amine hydration dynamics.

Water Arrangements upon Interaction with a Rigid Solute: Multiconfigurational Fenchone-(H2O)4-7 Hydrates.

Insight into the arrangements of water molecules around solutes is important to understand how solvation proceeds and to build reliable models to describe water-solute interactions. We report the stepwise solvation of fenchone, a biogenic ketone, with 4-7 water molecules. Multiple hydrates were observed using broadband rotational spectroscopy, and the configurations of four fenchone-(H2O)4, three fenchone-(H2O)5, two fenchone-(H2O)6, and one fenchone-(H2O)7 complexes were characterized from the analysis of their rotational spectra in combination with quantum-chemical calculations. Interactions with fenchone deeply perturb water configurations compared with the pure water tetramer and pentamer. In two fenchone-(H2O)4 complexes, the water tetramer adopts completely new arrangements, and in fenchone-(H2O)5, the water pentamer is no longer close to being planar. The water hexamer interacts with fenchone as the least abundant book isomer, while the water heptamer adopts a distorted prism structure, which forms a water cube when including the fenchone oxygen in the hydrogen bonding network. Differences in hydrogen bonding networks compared with those of pure water clusters show the influence of fenchone's topology. Specifically, all observed hydrates except one show two water molecules binding to fenchone through each oxygen lone pair. The observation of several water arrangements for fenchone-(H2O)4-7 complexes highlights water adaptability and provides insight into the solvation process.

Interactions of limonene with the water dimer.

The interactions of two molecules of water with the terpene limonene are characterised by chirped-pulse Fourier transform microwave spectroscopy. Seven isomers of limonene-(H2O)2 have been observed, and identified from the comparison of their experimental spectroscopic parameters with those predicted by computational methods. In all isomers a distorted water dimer binds to limonene through O-H⋯π and C-H⋯O interactions, and shows a strong preference for interacting with equatorial conformations of limonene. O-H⋯π hydrogen bonds to both endocyclic and exocyclic double bonds of limonene are established. In one of the isomers the water dimer forms a bridge between the endocyclic and exocyclic double bonds of limonene. Our results help advance our understanding of the interactions of water with atmospheric compounds.

New Insights into Secondary Organic Aerosol Formation: Water Binding to Limonene.

Limonene is an abundant monoterpene in the atmosphere and one of the main precursors of secondary organic aerosol. Understanding its interactions with atmospheric molecules is crucial to explain aerosol formation and the various products obtained from competing reaction pathways. Here, using broadband rotational spectroscopy in combination with computational calculations, we show that limonene effectively interacts with water, forming a variety of complexes. Seven different isomers of limonene-H2O, where water and limonene are connected by O-H···π and C-H···O interactions, have been unambiguously identified. Water has been found to preferentially bind to the endocyclic double bond of limonene. Our findings demonstrate a striking ability of water to attach to limonene and enrich our knowledge on the possible interactions of limonene in the atmosphere.