Premium
Intermolecular hydrogen bond energies in crystals evaluated using electron density properties: DFT computations with periodic boundary conditions
Author(s) -
Vener M. V.,
Egorova A. N.,
Churakov A. V.,
Tsirelson V. G.
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23062
Subject(s) - hydrogen bond , chemistry , intermolecular force , bond energy , periodic boundary conditions , basis set , thermodynamics , electron density , kinetic energy , density functional theory , computational chemistry , crystallography , computation , molecule , boundary value problem , electron , physics , mathematics , quantum mechanics , organic chemistry , algorithm
Abstract The hydrogen bond (H‐bond) energies are evaluated for 18 molecular crystals with 28 moderate and strong OH···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. © 2012 Wiley Periodicals, Inc.