Interaction between water and carbon nanostructures: How good are current density functional approximations?
Interaction between water and carbon nanostructures: How good are current density functional approximations?
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DOI：
10.1063/1.5121370
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发表时间：
2019-10-28
影响因子：
4.4
通讯作者：
Michaelides, Angelos
中科院分区：
文献类型：
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作者：
Brandenburg, Jan Gerit;Zen, Andrea;Michaelides, Angelos
由于其当前和未来的技术应用，包括水过滤器和海水淡化膜的实现，石墨sp(2)键合碳上的水吸附引起了人们极大的兴趣。然而，这些系统的建模非常具有挑战性，即使对于密度泛函理论 (DFT) 等电子结构方法也是如此，因为一般来说，伦敦色散力和非共价相互作用发挥着至关重要的作用。最近的努力已经建立了几种碳纳米结构与水相互作用的参考质量相互作用。在这里，我们编制了一个新的基准集（称为 WaC18），其中包括与各种碳结构和各种块状（3D）和二维（2D）冰多晶型物相互作用的单个水分子。通过计算与参考相互作用能的偏差来测试 28 种方法的性能，包括半局域交换相关函数、非局域 (Fock) 交换贡献和远程范德华 (vdW) 处理。 WaC18 集上计算的平均绝对偏差主要取决于 DFT 方法，范围从局部密度近似 (LDA) 的 135 meV 到 PBE0-D4 的 12 meV。我们发现现代 vdW 对 DFT 的修正比其前身有显着改善。在 28 种测试方法中，我们确定了广义梯度近似 (GGA)、meta-GGA、vdW-DF 和混合 DF 功能类别中表现最佳的方法，分别是 BLYP-D4、TPSS-D4、rev-vdW-DF2 和 PBE0-D4。由 AIP Publishing 许可发布。
Due to their current and future technological applications, including realization of water filters and desalination membranes, water adsorption on graphitic sp(2)-bonded carbon is of overwhelming interest. However, these systems are notoriously challenging to model, even for electronic structure methods such as density functional theory (DFT), because of the crucial role played by London dispersion forces and noncovalent interactions, in general. Recent efforts have established reference quality interactions of several carbon nanostructures interacting with water. Here, we compile a new benchmark set (dubbed WaC18), which includes a single water molecule interacting with a broad range of carbon structures and various bulk (3D) and two-dimensional (2D) ice polymorphs. The performance of 28 approaches, including semilocal exchange-correlation functionals, nonlocal (Fock) exchange contributions, and long-range van der Waals (vdW) treatments, is tested by computing the deviations from the reference interaction energies. The calculated mean absolute deviations on the WaC18 set depend crucially on the DFT approach, ranging from 135 meV for local density approximation (LDA) to 12 meV for PBE0-D4. We find that modern vdW corrections to DFT significantly improve over their precursors. Within the 28 tested approaches, we identify the best performing within the functional classes of generalized gradient approximated (GGA), meta-GGA, vdW-DF, and hybrid DF, which are BLYP-D4, TPSS-D4, rev-vdW-DF2, and PBE0-D4, respectively. Published under license by AIP Publishing.