Assessment of ten DFT methods in predicting structures of sheet silicates: Importance of dispersion corrections

Abstract

The performance of ten density functional theory (DFT) methods in a prediction of the structure of four clay minerals, in which non-bonding interactions dominate in the layer stacking (dispersive forces in talc and pyrophyllite, and hydrogen bonds in lizardite and kaolinite), is reported. In a set of DFT methods following functionals were included: standard local and semi-local (LDA, PW91, PBE, and RPBE), dispersion corrected (PW91-D2, PBE-D2, RPBE-D2, and vdW-TS), and functionals developed specifically for solids and solid surfaces (PBEsol and AM05). We have shown that the standard DFT functionals fail in the correct prediction of the structural parameters, for which non-bonding interactions are important. The remarkable improvement leading to very good agreement with experimental structures is achieved if the dispersion corrections are included in the DFT calculations. In such cases the relative error for the most sensitive lattice vector c dropped below 1%. Very good performance was also observed for both DFT functionals developed for solids. Especially, the results achieved with the PBEsol are qualitatively similar to those with DFT-D2.

DFT Study of Polymorphism in Al(OH)3: A Structural Synthon Approach

“…A similar trend was reported in sheet silicates by Tunega and co-workers. [35] Further, as observed in earlier reports, gibbsite is found to be the most stable structure among the four polymorphs of Al(OH) 3 . The energies of the other polymorphs are 0.60 eV (bayerite), 0.79 eV (nordstrandite), and 0.88 eV (doyleite), higher than the energy of the gibbsite, making doyleite the least stable polymorph.…”

DFT-based evaluation of porous metal formates for the storage and separation of small molecules

“…Preliminary optimisations that included a relaxation of the lattice parameters led to rather large deviations in the lattice dimensions, with maximum deviations of a few per cent for some metal formates that contain transition metals (the capabilities and limitations of DFT/DFT-D with regard to the accurate prediction of M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 8 lattice parameters have been subject of a number of computational studies, e.g. [46,47]). …”

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

“…Some characteristic structural parameters are listed in Table I for the three different configurations. Although the PBE-D2 geometries are not benchmark accuracy, there have been various studies on polymer crystals and layered materials, [105][106][107] and even for water on graphene, 28 indicating that PBE-D2 can provide reasonable structures for weakly interacting systems. Interested readers may also refer to the supplementary material 108 for bond lengths as well as the structures of fully relaxed complexes with MP2 and several of the xc functionals that we test.…”