吸附一氧化碳振动响应中气相非谐性的恢复和电条件下的击穿
Resilience of gas-phase anharmonicity in the vibrational response of adsorbed carbon monoxide and breakdown under electrical conditions
摘要：
在表面催化中，一氧化碳在过渡金属电极上的吸附代表了强化学吸附的原型。尽管吸附的CO的分子轨道的显着变化，光谱实验突出了吸附物的拉伸频率和平衡键长之间的密切相关性，为广泛的吸附几何形状和基板组合物。在这项工作中，我们研究了这种相关性的起源，通常被称为獾的规则，通过去卷积和检查的贡献，从吸附环境的分子内电位使用第一性原理计算。注意到分子内的非谐性保留CO化学吸附后，我们表明，獾的规则吸附CO可以表示单独的孤立CO的赫兹伯格光谱常数的列表。此外，虽然它已经建立了以前使用有限集群模型，獾的规则是不受电条件，我们发现，当带电表面被表示为周期性板时，Badger法则失效。从有效表面电荷的非谐贡献方面研究这种击穿揭示了传统有限簇模型在描述金属电极处的电条件时的局限性。
英文摘要：
In surface catalysis, the adsorption of carbon monoxide on transition-metal electrodes represents the prototype of strong chemisorption. Notwithstanding significant changes in the molecular orbitals of adsorbed CO, spectroscopic experiments highlight a close correlation between the adsorbate stretching frequency and equilibrium bond length for a wide range of adsorption geometries and substrate compositions. In this work, we study the origins of this correlation, commonly known as Badger's rule, by deconvoluting and examining contributions from the adsorption environment to the intramolecular potential using first-principles calculations. Noting that intramolecular anharmonicity is preserved upon CO chemisorption, we show that Badger's rule for adsorbed CO can be expressed solely in terms of the tabulated Herzberg spectroscopic constants of isolated CO. Moreover, although it had been previously established using finite-cluster models that Badger's rule is not affected by electrical conditions, we find here that Badger's rule breaks down when the electrified surface is represented as a periodic slab. Examining this breakdown in terms of anharmonic contributions from the effective surface charge reveals limitations of conventional finite-cluster models in describing electrical conditions at metal electrodes.
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