Orientational Water Bonding on Pt(111): Beyond the Frontier Orbital Principle,Langmuir

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Orientational Water Bonding on Pt(111): Beyond the Frontier Orbital Principle
Langmuir ( IF 3.7 ) Pub Date : 2023-07-26 , DOI: 10.1021/acs.langmuir.3c01545
Haochang Deng ₁ , Yongli Huang ₁ , Jibiao Li ₂

Affiliation

For decades, our understanding of water–metal bonding has been dominated by the frontier orbital principle in which globally stable water–metal interactions are ruled by HOMO interacting with metal surfaces. Using density functional theory calculations, herein, we have revealed that the frontier orbital principle cannot be applied to metastable water bonding on Pt(111), where the decisive role of HOMO is replaced by HOMO-1 in terms of the greatest orbital shifts and depopulations as the two different bonding indicators. Unlike the stable water configuration in which both HOMO-1 and HOMO prefer to overlap with metal states through σ-like orbital interactions, metastable configurations exhibit delicate competition or balance between σ-like and π-like orbital interactions exerted by HOMO-1 and HOMO, respectively. These findings have significantly deepened our understanding of orbital roles in water–metal bonding interactions and bridged the gap between theoretical understanding of electrified waters at electrochemical interfaces and water science on metal surfaces.

中文翻译：

Pt(111) 上的定向水键合：超越边界轨道原理

几十年来，我们对水-金属键合的理解一直由前沿轨道原理主导，其中全局稳定的水-金属相互作用由与金属表面的 HOMO 相互作用决定。通过密度泛函理论计算，我们发现前沿轨道原理不能应用于 Pt(111) 上的亚稳态水键合，其中 HOMO 在最大轨道位移和人口减少方面的决定性作用被 HOMO-1 取代作为两个不同的粘合指标。与HOMO-1和HOMO都喜欢通过类σ轨道相互作用与金属态重叠的稳定水构型不同，亚稳态构型在HOMO-1和HOMO施加的类σ和类π轨道相互作用之间表现出微妙的竞争或平衡，分别。这些发现极大地加深了我们对水-金属键合相互作用中轨道作用的理解，并弥合了电化学界面带电水的理论理解与金属表面水科学之间的差距。

更新日期：2023-07-26

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