Hydrogen bond detection.

In this Article we extend the idea of detecting a hydrogen bond solely on one single quantum chemically determined descriptor. We present an improvement of the method introduced by Reiher et al. (Theor. Chim. Acta 2001, 106, 379), who mapped the strength of the hydrogen bond onto an easily accessible quantity, namely, the two-center shared-electron number sigma(HA). First, we show that the linear dependence between the interaction energy from the supermolecular approach and sigma(HA) is valid for a test set of about 120 hydrogen-bonded complexes. Furthermore, we demonstrate that a classification according to acceptor atoms of the hydrogen-bonded complexes can give more accurate results. We thus recommend to detect hydrogen bonds with a specific acceptor atom according to our subset linear regression analysis. Case studies on alcohols and isolated base pairs and trimers from RNA and DNA show the utility of the detection criterion. The shared-electron number method yields that the strength of the N1...N3 hydrogen bond is in the range of 30 kJ/mol. Furthermore the A-U pair is indeed stronger bound than the A-T complex if environmental effects are incorporated in the calculations.