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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Geometrical correction for the inter- and intramolecular basis set superposition error in periodic density functional theory calculations
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Geometrical correction for the inter- and intramolecular basis set superposition error in periodic density functional theory calculations

机译：周期性密度泛函理论计算中分子间和分子内基集叠加误差的几何校正

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摘要

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 ? 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.
机译：我们将先前开发的分子间和分子内基集叠加误差（gCP）的几何校正扩展到周期性密度泛函理论（DFT）计算。我们报告的gCP结果与标准Boys-Bernardi平衡校正方案和大型基础集计算的结果相比。对于基准组X23，测试了该方法对分子晶体作为主要目标的适用性。它由Johnson等人介绍的23种非共价键结合的晶体组成。 （J.Chem.Phys.2012，137，054103），并由Tkatchenko等人精制。 （J.Chem.Phys.2013，139，024705）。为了准确描述远距离电子相关效应，我们使用标准的原子对色散校正方案DFT-D3。我们证明了DFT能量与小原子中心基集，D3色散校正和gCP校正的组合可以准确地描述范德华和氢键晶体。对于标准官能团PBE和B3LYP，X23升华能量的平均绝对偏差可以分别降低70％和80％以上，只有约2 kcal / mol的较小残留平均绝对偏差（相当于平均升华量的13％）能源）。作为进一步的测试，我们计算了不同距离下石墨的层间相互作用，并获得了良好的平衡距离和6.75？的相互作用能。在PBE-D3-gCP / SVP水平上为-43.0 meV /原子。我们将gCP方案适合于最近开发的pob-TZVP固态基础集，并获得X23基准集和水在镍（110）表面上吸附的势能曲线的合理结果。

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