Weaker intermolecular forces expand the isomerization alternatives for molecular aggregation, as observed for the prototype models of the aniline trimer (An3 ) and the monohydrated aniline dimer (An2 -W) when compared to the phenol trimer. In this experiment the aniline clusters were generated in a jet-cooled expansion and probed using broadband (chirped-pulsed) microwave spectroscopy. Three isomers of the aniline trimer and two isomers of the hydrated dimer were detected and characterized in the rotational spectrum. In the homotrimer the weak N-H⋅⋅⋅N hydrogen bonds are assisted by subtle combinations of N-H⋅⋅⋅π and C-H⋅⋅⋅π interactions, producing several competing low-lying ring species in the gas phase. One of the aniline trimers is a symmetric top, topologically equivalent to the only observed phenol trimer. Conversely, addition of a water molecule to the aniline dimer introduces a leading O-H⋅⋅⋅N interaction, making water to behave as dominant hydrogen-bond pivot between the two aniline molecules. This combination of weak intermolecular interactions critically tests the performance of dispersion-corrected or parametrized density-functional methods. Evaluation of the B3LYP-D3(BJ) and M06-2X methods revealed deficiencies of the Truhlar functional to reproduce the experimental rotational data.
Keywords: aniline trimer; rotational spectroscopy; supersonic jets; weak hydrogen bonding.
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