R. Parra, Mako Furukawa, B. Gong
Sep 17, 2001
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0
Influential Citations
44
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Journal
Journal of Chemical Physics
Abstract
High level ab initio calculations are carried out on diacetamide–X (DA–X) dimers, X=HCN, CH3OH. The dimers are used as model systems to investigate the energetics and cooperative phenomomena in intermolecular three-center hydrogen-bond (H-bond) interactions relative to two-center H-bond interactions. The trans–trans conformer of diacetamide is chosen as a suitable model for intermolecular three-center H bonding where one H atom is interacting with two acceptor atoms. The proton–acceptor atoms are rigidly held in the same molecule. For both model systems, it is found that the calculated interaction energy per H bond is appreciably smaller in the three-center than in the two-center H-bond dimers, suggesting possibly a general characteristic of intermolecular three-center H bonds, namely, a negative cooperativity. More importantly, it is found that frequency shifts, intensity factors, bond lengths, and 1H nuclear magnetic resonance chemical shifts all support the energetic calculations in that the intermolec...