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Water self-association dominates the formation of microsolvated molecular clusters which may give rise to complex structures resembling those of pure water clusters. We present a rotational study of the complex formamide-(H 2 O) 3 formed in a supersonic jet and several monosubstituted isotopologues. Formamide and water molecules form a four-body sequential cycle through N-H···O, O-H···O, and O-H···O═C hydrogen bonds, resulting in a chiral structure with a nonplanar skeleton that can be overlapped to that of water pentamer. The analysis of the 14 N-nucleus quadrupole coupling effects shows the depletion of the electron density of the N atom lone pair with respect to the bare formamide that affects the amide group C-N and C═O distances. The study of the observed tunneling doublets shows that formamide-(H 2 O) 3 follows a path to invert its structure driven by the flipping of water subunits and passing through successive nonplanar configurations, a motion reminiscent of the pseudorotation of water pentamer.

Structure and Dynamics in Formamide–(H2O)3: A Water Pentamer Analogue

Structure and Dynamics in Formamide–(H₂O)₃: A Water Pentamer Analogue