Chemistry and Chemical Biology, School of Natural Sciences, University of California, Merced, 5200 North Lake Road, Merced, California 95343, USA.
J Chem Phys. 2012 Aug 7;137(5):054103. doi: 10.1063/1.4738961.
A benchmark for non-covalent interactions in solids (C21) based on the experimental sublimation enthalpies and geometries of 21 molecular crystals is presented. Thermal and zero-point effects are carefully accounted for and reference lattice energies and thermal pressures are provided, which allow dispersion-corrected density functionals to be assessed in a straightforward way. Other thermal corrections to the sublimation enthalpy (the 2RT term) are reexamined. We compare the recently implemented exchange-hole dipole moment (XDM) model with other approaches in the literature to find that XDM roughly doubles the accuracy of DFT-D2 and non-local functionals in computed lattice energies (4.8 kJ/mol mean absolute error) while, at the same time, predicting cell geometries within less than 2% of the experimental result on average. The XDM model of dispersion interactions is confirmed as a very promising approach in solid-state applications.
本文提出了一个基于 21 种分子晶体实验升华焓和几何形状的固态非共价相互作用基准（C21）。本文仔细考虑了热和零点能效应，并提供了参考晶格能和热压，这使得可以直接评估色散校正密度泛函。对升华焓的其他热修正（2RT 项）进行了重新检查。我们将最近实现的交换空穴偶极矩（XDM）模型与文献中的其他方法进行了比较，发现 XDM 大致将 DFT-D2 和非局部泛函在计算晶格能时的准确性提高了一倍（平均绝对误差为 4.8 kJ/mol），同时，平均而言，预测的晶胞几何形状与实验结果的误差小于 2%。色散相互作用的 XDM 模型被证实是固态应用中很有前途的方法。
