Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie der Universität Bonn , Beringstraße 4, 53115 Bonn, Germany.
J Phys Chem A. 2013 Sep 26;117(38):9282-92. doi: 10.1021/jp406658y. Epub 2013 Sep 13.
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-Bernardi 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 Å and -43.0 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.
我们将之前开发的用于校正分子内和分子间基组重叠误差（gCP）的几何校正方法扩展到周期性密度泛函理论（DFT）计算中。我们报告了 gCP 结果，并与标准的 Boys-Bernardi 对消校正方案和大基组计算结果进行了比较。该方法的适用性作为主要目标，在基准集 X23 上进行了测试。它由 Johnson 等人（J. Chem. Phys. 2012, 137, 054103）引入的 23 个非共价键结合晶体组成，并由 Tkatchenko 等人（J. Chem. Phys. 2013, 139, 024705）进行了修正。为了准确描述长程电子相关效应，我们使用了标准的原子对色散校正方案 DFT-D3。我们表明，DFT 能量与小原子中心基组、D3 色散校正和 gCP 校正的组合可以准确描述范德华和氢键晶体。对于标准泛函 PBE 和 B3LYP，X23 升华能的平均绝对偏差分别可以减少 70%和 80%以上，得到约 2 kcal/mol 的小残余平均绝对偏差（对应于平均升华能的 13%）。作为进一步的测试，我们计算了石墨的层间相互作用随距离的变化，并在 PBE-D3-gCP/SVP 水平上得到了 6.75 Å 和-43.0 meV/原子的良好平衡距离和相互作用能。我们拟合了最近开发的 pob-TZVP 固态基组的 gCP 方案，并对 X23 基准集和水在镍（110）表面吸附的势能曲线得到了合理的结果。
