Application of semiempirical long‐range dispersion corrections to periodic systems in density functional theory

Abstract

Ewald summation is used to apply semiempirical long-range dispersion corrections (Grimme, J Comput Chem 2006, 27, 1787; 2004, 25, 1463) to periodic systems in density functional theory. Using the parameters determined before for molecules and the Perdew-Burke-Ernzerhof functional, structure parameters and binding energies for solid methane, graphite, and vanadium pentoxide are determined in close agreement with observed values. For methane, a lattice constant a of 580 pm and a sublimation energy of 11 kJ mol(-1) are calculated. For the layered solids graphite and vanadia, the interlayer distances are 320 pm and 450 pm, respectively, whereas the graphite interlayer energy is -5.5 kJ mol(-1) per carbon atom and layer. Only when adding the semiempirical dispersion corrections, realistic values are obtained for the energies of adsorption of C(4) alkenes in microporous silica (-66 to -73 kJ mol(-1)) and the adsorption and chemisorption (alkoxide formation) of isobutene on acidic sites in the micropores of zeolite ferrierite (-78 to -94 kJ mol(-1)). As expected, errors due to missing self-interaction correction as in the energy for the proton transfer from the acidic site to the alkene forming a carbenium ion are not affected by the dispersion term. The adsorption and reaction energies are compared with the results from Møller-Plesset second-order perturbation theory with basis set extrapolation.

Tuning the electronic structure of ultrathin crystalline silica films on Ru(0001)

“…The calculated values of E adh are similar to those of other dispersion-bound systems, e.g., to the interlayer BE in bulk V 2 O 5 . 37 The (SiO 2 ) 8 /Ru structure with no interfacial oxygen atoms has the highest adhesion energy. Oxygen adsorption on the Ru(0001) surface considerably lowers the adhesion energy.…”

“…A semiempirical dispersion correction was added to qualitatively account for the dispersion forces (PBE + D). [35][36][37] Unless stated otherwise, a 400-eV cutoff for the plane wave basis set and a (8 × 4 × 1) Monkhorst-Pack grid 38 for the integrations of the first Brillouin zone were used. The positions of nuclei were relaxed until the forces were smaller than 10 −3 eV/Å.…”

Theoretical Study of the Adsorption of the Butanol Isomers in H-ZSM-5

“…These alcohols are ideally suited to examine the H-ZSM-5 framework effects since (1) their dimensions are comparable to those of the H-ZSM-5 channels and (2) their hydrocarbon skeletons with different branching present a convenient testing group to explore the role of the molecular shape and structure in controlling the nature and stability of the adsorbed complexes. Because of the dominant stabilizing role of vdW interactions, the pbc[DFT-D] approach 33,34 in which the Grimme's dispersion correction 33 is included in the periodic DFT calculations 34 is used in the present work for obtaining optimized structures, energies, and for determining harmonic vibrational frequencies of the adsorbed systems. 35,36 show a variability of the Al siting for ZSM-5 samples with the Si/Al ratio of 95 (one Al per unit cell).…”

Role of van der Waals bonding in the layered oxideV2O5: First-principles density-functional calculations

“…Earlier, another group 19 has examined the role of the vdW forces in V 2 O 5 by means of the semiempirical DFT-D approach ͑Ref. 18͒, arriving at a similar conclusion.…”

“…18͒ for adding the vdW forces. 19 In this paper we use the first-principles vdW densityfunctional approach, vdW-DF, 20,21 to determine the V 2 O 5 bulk structure. We find that the vdW forces are indeed important for binding the structure, and we analyze the binding within and mainly between the layers.…”