Geometrical Correction for the Inter- and Intramolecular Basis Set Superposition Error in Periodic Density Functional Theory Calculations
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- 作者：Jan Gerit Brandenburg ; Maristella Alessio ; Bartolomeo Civalleri ; Michael F. Peintinger ; Thomas Bredow ; Stefan Grimme
- 刊名：Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：September 26, 2013
- 年：2013
- 卷：117
- 期：38
- 页码：9282-9292
- 全文大小：495K
- 年卷期：v.117,no.38(September 26, 2013)
- ISSN：1520-5215
文摘
We extend the previously developed geometrical correction for the inter- and intramolecular basis set superposition error (gCP) to periodic density functional theory (DFT) calculations. We report gCP results compared to those from the standard Boys鈥揃ernardi counterpoise correction scheme and large basis set calculations. The applicability of the method to molecular crystals as the main target is tested for the benchmark set X23. It consists of 23 noncovalently bound crystals as introduced by Johnson et al. ( J. Chem. Phys. 2012, 137, 054103) and refined by Tkatchenko et al. ( J. Chem. Phys. 2013, 139, 024705). In order to accurately describe long-range electron correlation effects, we use the standard atom-pairwise dispersion correction scheme DFT-D3. We show that a combination of DFT energies with small atom-centered basis sets, the D3 dispersion correction, and the gCP correction can accurately describe van der Waals and hydrogen-bonded crystals. Mean absolute deviations of the X23 sublimation energies can be reduced by more than 70% and 80% for the standard functionals PBE and B3LYP, respectively, to small residual mean absolute deviations of about 2 kcal/mol (corresponding to 13% of the average sublimation energy). As a further test, we compute the interlayer interaction of graphite for varying distances and obtain a good equilibrium distance and interaction energy of 6.75 脜 and 鈭?3.0 meV/atom at the PBE-D3-gCP/SVP level. We fit the gCP scheme for a recently developed pob-TZVP solid-state basis set and obtain reasonable results for the X23 benchmark set and the potential energy curve for water adsorption on a nickel (110) surface.