Theory meets experiment for elucidating the structure and stability of non-covalent complexes: water-amine interaction as a proof of concept

Abstract

Several gas-phase spectroscopic investigations have focused on a better understanding of the nature of weak, non-covalent interactions in model systems. However, their characterization and interpretation are still far from being satisfactory. A promising route to fill this gap is offered by strategies in which high-resolution rotational spectroscopy is deeply integrated with state-of-the-art quantum-chemical methodology to accurately determine intermolecular parameters and interaction energies, with the latter interpreted by means of powerful energy decomposition analyses (EDAs). As a proof of concept of this approach, we have selected the adducts formed by n-propylamine (PA) and iso-propylamine (IPA) with water. Among the stable structures computationally predicted, four (out of five) isomers of the PA-water complex and two isomers (trans and gauche) of the IPA-water adduct have been characterized with supersonic jet Fourier transform microwave spectroscopy. Starting from the experimental rotational constants for different isotopic species, computation of the corresponding vibrational corrections allowed a semi-experimental determination of the intermolecular parameters. Different EDAs point out that in all cases a strong O-HN hydrogen bond is the primary interaction. Accurate computations indicate that the length and ramification of the alkyl chain do not significantly affect the water-amine interactions, which - on the contrary - modify the stability order of PA conformers with respect to the isolated systems.