The hydrogen bond (H-bond) energies are evaluated for 18 molecular crystals with 28 moderate and strong O-H···O bonds using the approaches based on the electron density properties, which are derived from the B3LYP/6-311G** calculations with periodic boundary conditions. The approaches considered explore linear relationships between the local electronic kinetic G(b) and potential V(b) densities at the H···O bond critical point and the H-bond energy E(HB). Comparison of the computed E(HB) values with the experimental data and enthalpies evaluated using the empirical correlation of spectral and thermodynamic parameters (Iogansen, Spectrochim. Acta Part A 1999, 55, 1585) enables to estimate the accuracy and applicability limits of the approaches used. The V(b)-E(HB) approach overestimates the energy of moderate H-bonds (E(HB) < 60 kJ/mol) by ~20% and gives unreliably high energies for crystals with strong H-bonds. On the other hand, the G(b)-E(HB) approach affords reliable results for the crystals under consideration. The linear relationship between G(b) and E(HB) is basis set superposition error (BSSE) free and allows to estimate the H-bond energy without computing it by means of the supramolecular approach. Therefore, for the evaluation of H-bond energies in molecular crystals, the G(b) value can be recommended to be obtained from both density functional theory (DFT) computations with periodic boundary conditions and precise X-ray diffraction experiments.

The alanine (Ala)‐based cluster models of C5, C7, and C10 H‐bonds are studied at the DFT/B3LYP level. CPMD/BLYP simulations of the infinite polyalanine α‐helix (C13 H‐bond) and the two‐stranded β‐sheets are performed. Combined use of frequency shifts and electron‐density features enable us to detect and describe quantitatively the non‐covalent interactions (H‐bonds) defining the intrinsic properties of Ala‐based secondary structures. The energies of the primary NH$\cdots $O H‐bonds are decreasing in the following way: C13 > C5 ≥ C7 > C10. The energies of the secondary NH$\cdots $O, N−H$\cdots $N, and H$\cdots $H interactions are comparable to those of the primary H‐bonds (∼4.5 kcal/mol). Side chain–backbone CH$\cdots $O interaction is found to be the weakest non‐covalent interaction in the considered species. Its energy is ∼0.5 kcal/mol in the infinite polyalanine α‐helix. Quantum‐topological electron‐density analysis is found to be a powerful tool for the detection of secondary non‐covalent interactions (CO$\cdots $HC and H$\cdots $H) and bifurcated H‐bonds, while the frequency shift study is useful for the identification and characterization of primary or secondary H‐bonds of the NH$\cdots $O type. Copyright © 2008 John Wiley & Sons, Ltd.

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By the methods of MALDI and mass spectroscopy with the detection of positively and negatively charged ions, it was found that the reaction of elemental sulfur and 1,3-dimethylimidazolium dimethylphosphate is accompanied by the opening of the S8 ring. 1H, 13C, 15N and 31P NMR spectroscopy showed that the interaction of S8 and 1,3-dimethylimidazolium dimethylphosphate proceeds exclusively on the oxygen atom of the dimethylphosphate anion carrying a negative charge. Kohn-Sham calculations at B3LYP/STO-3G, B3LYP/6-31G* and B3LYP/6-311G* levels of theory confirmed that the reaction of S8 with dimethylphosphate anion is possible.

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