Trends in adsorption characteristics of benzene on transition metal surfaces: Role of surface chemistry and van der Waals interactions
Trends in adsorption characteristics of benzene on transition metal surfaces: Role of surface chemistry and van der Waals interactions
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苯在过渡金属表面吸附特性的趋势：表面化学和范德华相互作用的作用
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发表时间：
2017
期刊：
影响因子：
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通讯作者：
A. Kara
中科院分区：
文献类型：
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作者：
T. Greber;A. Kara
有机分子与金属表面界面特性的准确描述一直是理论研究中的热点问题。对于这些混合的无机/有机界面来说，对界面几何形状和吸附能的良好描述是非常必要的。采用包含五个van der Waals泛函的第一性原理计算(VDW-DF家族)，研究了苯(C6H6)在七种过渡金属表面的吸附，以探讨这些VDW泛函在不同表面化学条件下的性能。我们的结果表明，VDW相互作用对于准确描述过渡金属衬底上的成键至关重要。我们发现，VDW相互作用使铸币金属表面(Au，Ag，Cu)的吸附能增加了约0.7 eV，而它们导致了反应性过渡金属表面(Pd，Pt，Rh，Ni)的吸附能更大的增加。我们的计算还表明，由VDW泛函引起的吸附能变化表现出显著的变化，并且可以归类。我们发现，用VDW-DF和VDW-DF2泛函得到的反应性过渡金属表面的吸附能和吸附高度与OPT型泛函有很大的不同，揭示了前者在短距离内的本征强排斥特性。实验测定的吸附能(平均值)与计算值的简单比较表明，optPBE泛函和optB88泛函具有较好的一致性。我们从这些泛函的性能分析中获得的信息可以作为进一步改进这些吸附泛函的基础。摘要有机分子与金属表面之间的界面特征的准确描述在理论研究中一直是争论的焦点。所有提出的方法都揭示了范德华相互作用的重要性。采用第一性原理计算方法，研究了苯(C6H6)在铸币表面和过渡金属表面的吸附行为，探讨了这些泛函在不同表面化学条件下的吸附行为。我们的结果表明，范德华相互作用不仅对硬币成键，而且对过渡金属衬底成键的准确描述都是至关重要的。此外，这五个泛函的吸附能结果显示出显著的差异，有一种趋势是允许根据计算的吸附强度进行分组。实验测定的平均吸附能与计算值的简单比较表明，optPBE和optB88泛函表现出较好的系统一致性。从我们对这些官能团的性能的综合分析中获得的信息引起了广泛的兴趣，特别是可以作为进一步完善这些官能团以适应不同的表面化学的基础。
: The accurate description of interface characteristics between organic molecules and metal surfaces has long been debated in theoretical studies. A well-founded description of interface geometry and adsorption energy is highly desirable for these hybrid inorganic/organic interfaces. Using first principles calculations with the inclusion of five van der Waals functionals (vdW-DF family), benzene (C6H6) adsorption on seven transition metal surfaces is studied to explore the performance of these vdW functionals under varying surface chemistry. Our results reveal that vdW interactions are crucial for an accurate description of bonding on transition metal substrates. We find that vdW interactions increase adsorption energy on coinage metal surfaces (Au, Ag, Cu) by about 0.7 eV, while they lead to even larger increases in the adsorption energies on the reactive transition metal surfaces (Pd, Pt, Rh, Ni). Our calculations also reveal that changes in adsorption energies stemming from vdW functionals show significant variation, and can be grouped. We find the adsorption energies and heights on the reactive transition metal surfaces obtained using vdW-DF and vdW-DF2 functionals to differ significantly from those of the opt-type functionals, revealing the intrinsic strong repulsion character at short ranges for the former functionals. A simple comparison between experimentally determined adsorption energies (averaged) and those of computed suggests that optPBE and optB88 functionals show systematically good agreement. The information acquired from our analysis on the performance of these functionals can be used as a basis for further refinement of these functionals for the adsorption Abstract The accurate description of interface characteristics between organic molecules and metal surfaces has long been debated in theoretical studies. All proposed methods revealed the importance of van der Waals interactions. Using first principles calculations with the inclusion of five van der Waals functionals, Benzene (C 6 H 6 ) adsorption on coinage and transition metal surfaces are studied to explore the performance of these functionals under varying surface chemistries. Our results reveal that van der Waals interactions are crucial for an accurate description of bonding not only for coinage, but also for transition metal substrates. Moreover, adsorption energy results stemming from these five functionals show significant variation, with a trend that allows a grouping based on the calculated adsorption strengths. A simple comparison between the averaged experimentally determined adsorption energies and those computed suggests that optPBE and optB88 functionals show systematically good agreements. The information acquired from our comprehensive analysis on the performance of these functionals is of broad interest, and in particular, can be used as a basis for further refinement of these functionals for varying surface chemistry.