期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 29, 期 13, 页码 2088-2097出版社
WILEY
DOI: 10.1002/jcc.21069
关键词
density functional theory; dispersion energy; CH4; graphite; V2O5; hydrocarbon; adsorption; silica; zeolite
资金
- Deutsche Forschungsgemeinschaft
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 formin a carbenium ion are not affected by the dispersion term. The adsorption and reaction energies are compared with the results from Moller-Plesset second-order perturbation theory with basis set extrapolation. (C) 2008 Wiley Periodicals. Inc.
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