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

✍ Scribed by Torsten Kerber; Marek Sierka; Joachim Sauer

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 258 KB
• Volume: 29
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21069

✦ Synopsis

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. © 2008 Wiley Periodicals, Inc. J Comput Chem 2008