基于DFT的更准确的吸附能方法：来自RPBE和vdW密度泛函的自适应能量总和,The Journal of Physical Chemistry C

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基于DFT的更准确的吸附能方法：来自RPBE和vdW密度泛函的自适应能量总和
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2017-02-27 00:00:00 , DOI: 10.1021/acs.jpcc.6b10187
Alyssa J. R. Hensley ₁ , Kushal Ghale ₂ , Carolin Rieg ₁ , Thanh Dang ₂ , Emily Anderst ₁ , Felix Studt ₃ , Charles T. Campbell ₄ , Jean-Sabin McEwen _{1,

5} , Ye Xu ₂

Affiliation

近年来，随着功能边界材料的设计和优化，具有周期性边界条件的密度泛函理论（DFT）迅速普及。但是，当与表面的键合以强共价键或离子键为主且当范德华相互作用（即分散力）有很大贡献时，当前没有可用的DFT交换相关函数在过渡金属上提供准确的吸附能。在这里，我们介绍了一种新的简单方法，该方法基于RPBE和optB86b-vdW（或optB88-vdW）密度泛函的能量自适应加权总和，基于DFT计算精确预测过渡金属表面上的吸附能。该方法已针对39种可靠的吸附反应实验能量进行了基准测试。我们的结果表明，相对于BEEF-vdW功能的20.4和26.4 kJ / mol，该方法相对于实验分别具有13.4 kJ / mol和19.3 kJ / mol的平均绝对误差和均方根误差。对于范德华贡献较大的系统，此方法可将这些误差降低到11.6和17.5 kJ / mol。因此，该方法提供了对于以强共价键或离子键为主导的过程以及以分散力为主导的过程的吸附能的预测，这些比单独的任何当前标准DFT功能更精确。6和17.5 kJ / mol。因此，该方法提供了对于以强共价键或离子键为主导的过程以及以分散力为主导的过程的吸附能的预测，这些比单独的任何当前标准DFT功能更精确。6和17.5 kJ / mol。因此，该方法提供了对于以强共价键或离子键为主导的过程以及以分散力为主导的过程的吸附能的预测，这些比单独的任何当前标准DFT功能更精确。

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DFT-Based Method for More Accurate Adsorption Energies: An Adaptive Sum of Energies from RPBE and vdW Density Functionals

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) density functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Thus, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.

更新日期：2017-02-27

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