A novel correction scheme for DFT: A combined vdW-DF/CCSD(T) approach

作者：Hermann Jan^*; Bludsky Ota

来源：Journal of Chemical Physics, 2013, 139(3): 034115.

DOI：10.1063/1.4813826

A system-specific but very accurate density functional theory (DFT) correction scheme is proposed for precise calculations of adsorbent-adsorbate interactions by combining the non-empirical van der Waals density functional (vdW-DF) method and the empirical DFT/CC correction scheme to reach accuracy of the coupled clusters method with single, double and perturbative triple excitations (CCSD(T)). The new approach is applied to small molecules (CH4, CO2, H-2, H2O, N-2) interacting with silica surfaces and purely siliceous microporous solids. The vdW-DF/CC results for a perfectly reconstructed a-quartz surface are consistent with other dispersion-corrected DFT methods. Corrected for ZPVE, the vdW-DF/CC enthalpies of adsorption in pure-silica zeolite LTA (Delta H-ads(0 K)) of 3.6 and 5.2 kcal/mol for methane and carbon dioxide, respectively, are in excellent agreement with experimental values of 3.6 and 5.0 kcal/mol. The very high accuracy of the new scheme and its relatively easy use and numerical stability as compared to the earlier DFT/CC scheme offer a straightforward solution for obtaining reliable predictions of adsorption energies.

• 出版日期2013-7-21