title: Estimating the energy of intramolecular hydrogen bonds from1H NMR and QTAIM calculations.
abstract: The values of the downfield chemical shift of the bridge hydrogen atom were estimated for a series of compounds containing an intramolecular hydrogen bond O-HO, O-HN, O-HHal, N-HO, N-HN, C-HO, C-HN and C-HHal. Based on these values, the empirical estimation of the hydrogen bond energy was obtained by using known relationships. For the compounds containing an intramolecular hydrogen bond, the DFT B3LYP/6-311++G(d,p) method was used both for geometry optimization and for QTAIM calculations of the topological parameters (electron density ρBCPand the density of potential energy V in the critical point of the hydrogen bond). The calculated geometric and topological parameters of hydrogen bonds were also used to evaluate the energy of the hydrogen bond based on the equations from the literature. Comparison of calibrating energies from the1H NMR data with the energies predicted by calculations showed that the most reliable are the linear dependence on the topological ρBCPand V parameters. However, the correct prediction of the hydrogen bond energy is determined by proper fitting of the linear regression coefficients. To obtain them, new linear relationships were found between the calculated ρBCPand V parameters and the hydrogen bond energies obtained from empirical1H NMR data. These relationships allow the comparison of the energies of different types of hydrogen bonds for various molecules and biological ensembles.
authors.affiliation: Institute of Chemistry, Siberian Division of Russian Academy of Sciences, 664033 Irkutsk, Russia. andvalaf@irioch.irk.ru.
authors.forename: Andrei V
authors.initials: AV
authors.lastname: Afonin
authors.affiliation: Institute of Chemistry, Siberian Division of Russian Academy of Sciences, 664033 Irkutsk, Russia. andvalaf@irioch.irk.ru.
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Vashchenko
authors.affiliation: Department of Chemistry, Ben-Gurion University of the Negev, 84104, Beer Sheva, Israel. msigalov@bgu.ac.il.
authors.forename: Mark V
authors.initials: MV
authors.lastname: Sigalov