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Quantitative Prediction of Molecular Adsorption: Structure and Binding of Benzene on Coinage Metals

机译:分子吸附的定量预测:苯在铸币金属上的结构与结合

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摘要

Interfaces between organic molecules and solid surfaces play a prominent role in heterogeneous catalysis, molecular sensors and switches, light-emitting diodes, and photovoltaics. The properties and the ensuing function of such hybrid interfaces often depend exponentially on molecular adsorption heights and binding strengths, calling for well-established benchmarks of these two quantities. Here we present systematic measurements that enable us to quantify the interaction of benzene with the Ag(111) coinage metal substrate with unprecedented accuracy (0.02 Å in the vertical adsorption height and 0.05 eV in the binding strength) by means of normal-incidence x-ray standing waves and temperature-programed desorption techniques. Based on these accurate experimental benchmarks for a prototypical molecule-solid interface, we demonstrate that recently developed first-principles calculations that explicitly account for the nonlocality of electronic exchange and correlation effects are able to determine the structure and stability of benzene on the Ag(111) surface within experimental error bars. Remarkably, such precise experiments and calculations demonstrate that despite different electronic properties of copper, silver, and gold, the binding strength of benzene is equal on the (111) surface of these three coinage metals. Our results suggest the existence of universal binding energy trends for aromatic molecules on surfaces.
机译:有机分子和固体表面之间的界面在非均相催化,分子传感器和开关,发光二极管和光伏发电中发挥着重要作用。这种杂化界面的性质和随后的功能通常成倍地取决于分子的吸附高度和结合强度,因此需要这两个量的公认基准。在这里,我们介绍了系统的测量方法,这些方法使我们能够通过正向入射x-量化苯与Ag(111)铸币金属基材之间的相互作用,具有前所未有的精度(垂直吸附高度0.02Å和结合强度0.05 eV)射线驻波和程序升温解吸技术。基于这些用于原型分子-固体界面的准确实验基准,我们证明了最近开发的第一性原理计算可以明确确定电子交换的非局限性和相关效应,从而能够确定苯在Ag上的结构和稳定性(111 )内的实验误差线。值得注意的是,这种精确的实验和计算表明,尽管铜,银和金的电子特性不同,但在这三种造币金属的(111)表面上苯的结合强度是相等的。我们的结果表明表面上芳香分子普遍存在结合能趋势。

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