Hydrogen bonding in diols and binary diol–water systems investigated using DFT methods. II. Calculated infrared OH‐stretch frequencies, force constants, and NMR chemical shifts correlate with hydrogen bond geometry and electron density topology. A reevaluation of geometrical criteria for hydrogen bo

Although the two hydroxyl groups in 1,2‐diols interact as evidenced by NMR and IR spectroscopic shifts, electron density topological analysis has shown a bond critical point (BCP) and atomic bond path to be absent (Klein, R. A.; J Comp Chem 2002, 23, 585–599; J Am Chem Soc 2002, 124, 13931–13937), indicating that no intramolecular hydrogen bond is formed. Here, we demonstrate that small NMR or IR shifts are neither necessarily diagnostic nor sufficient as indicators of hydrogen bond formation; moreover, modified van der Waals atomic radii are needed for estimating maximum nuclear interaction distances and nuclear interpenetration. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1120–1131, 2003

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