On the Accuracy of DFT for Describing Hydrogen Bonds:  Dependence on the Bond Directionality

Abstract

A set of representative hydrogen bonded dimers has been studied employing density functional theory (DFT) in the Perdew, Burke, and Ernzerhof (PBE) generalized gradient approximation. Our results for hydrogen bond (hb) strengths and geometry parameters show good agreement with those obtained by Møller-Plesset (MP2) or Coupled-Cluster (CC) methods. We observe that the reliability of DFT-PBE for the description of hbs is closely connected to the bond directionality (i.e. the angle between D-H and H‚‚‚A where D and A are the donor and the acceptor atoms or regions, respectively, in the hb interaction): with increasing deviation from a linear D-H‚‚‚A arrangement the accuracy of the DFT-PBE decreases.

Improved Density Functionals for Water

“…The authors found that the results obtained using the aug-cc-pV5Z basis set versus a plane wave basis set with an energy cutoff of 1000 eV (73.5 Ry) showed good agreement. Furthermore, Ireta et al 82 used the PBE functional and plane wave basis set, with a 70 Ry energy cutoff, to determine the binding energies for a set of representative hydrogen bonded dimers. The binding energies obtained were in excellent agreement with a separate study 37 that calculated the binding energies for the same dimers using the PBE functional and the MG3S basis set.…”

Elimination of basis set superposition error in linear-scaling density-functional calculations with local orbitals optimised in situ

“…The water dimer is bound by a medium strength hydrogen bond which has been important for the development of the theory of intermolecular forces and is seen as a paradigm of the bonding upon which many biochemical processes so sensitively depend. As a relatively weak bond, it is a challenge for DFT [24,25] and calculations of its binding energy are very sensitive to BSSE [26]. For the purposes of this study comparison is made with results from the BSSE-free plane-wave castep code [27] by varying the hydrogen bond O-H length d while the orientation and internal geometry of the water molecules remained fixed: structural rearrangements [28] are not considered.…”

Textured fluorapatite bonded to calcium sulphate strengthen stomatopod raptorial appendages

“…Computations indicated that the interface can be stabilized by a network of interphase hydrogen bonding between FAP and gypsum, suggesting that hydrogen bonding plays an important role in providing binding strength at the interface. The computations, which are based on the density functional theory whose capabilities have been used extensively to predict H-bonding network 39,40 , also show that the hydrogen bond network is mediated through the gypsum water molecules, suggesting that the hydration state of sulphate plays a specific stabilization role at the interface. To compare the influence of fluoride ions on interface stability, we computed the bond length and bond energies of both FAP/CAS and HAP/ CAS interfaces.…”