Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure.
Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure.
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吸附到 Ag(111) 表面的苯衍生物：结合位点和电子结构。
DOI：
10.1063/1.4908267
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
E. Zurek
中科院分区：
文献类型：
--
作者：
Daniel P. Miller;S. Simpson;Nina Tymińska;E. Zurek
采用色散校正密度泛函理论计算来研究用包含大面积活化/失活光谱的官能团衍生的苯对 Ag(111) 表面的吸附。被弱活化或失活基团（例如甲基和氟）取代的苯对吸附到基材上的特定位点没有强烈的偏好，势能表面的波纹与苯的波纹相似。另一方面，强活化基团 (N(CH3)2) 和失活基团 (NO2) 具有独特的位点偏好。前者中的氮更倾向于位于银原子上方（顶部位点），但后者更倾向于 Ag(111) 表面的中空六方密堆积 (Hhcp) 位点。用经典活化基团衍生的苯将电子密度从其最高占据的分子轨道提供给表面，而用失活基团官能化的苯则将电子密度从表面吸收到气相中未占据的轨道中。对于用两个取代基官能化的苯，强烈活化或失活的基团控制位点偏好，而其他基团所占据的位点在很大程度上由它们在苯环上的位置决定。在某些情况下，二取代苯的邻位、间位和对位异构体的相对稳定性可以通过吸附到表面来改变。
Dispersion corrected Density Functional Theory calculations were employed to study the adsorption of benzenes derivatized with functional groups encompassing a large region of the activated/deactivated spectrum to the Ag(111) surface. Benzenes substituted with weak activating or deactivating groups, such as methyl and fluoro, do not have a strong preference for adsorbing to a particular site on the substrate, with the corrugations in the potential energy surface being similar to those of benzene. Strong activating (N(CH3)2) and deactivating (NO2) groups, on the other hand, possess a distinct site preference. The nitrogen in the former prefers to lie above a silver atom (top site), but in the latter a hollow hexagonal-closed-packed (Hhcp) site of the Ag(111) surface is favored instead. Benzenes derivatized with classic activating groups donate electron density from their highest occupied molecular orbital to the surface, and those functionalized with deactivating groups withdraw electron density from the surface into orbitals that are unoccupied in the gas phase. For benzenes functionalized with two substituents, the groups that are strongly activating or deactivating control the site preference and the other groups assume sites that are, to a large degree, dictated by their positions on the benzene ring. The relative stabilities of the ortho, meta, and para positional isomers of disubstituted benzenes can, in some cases, be modified by adsorption to the surface.
同手性黄嘌呤五重网络在 Au(111) 表面上自组装。
影响因子：
17.1
作者：
Yu M
通讯作者：
Yu M
影响因子：
4.4
作者：
Carrasco, Javier;Liu, Wei;Tkatchenko, Alexandre
通讯作者：
Tkatchenko, Alexandre
影响因子：
4.4
作者：
Klimes, Jiri;Michaelides, Angelos
通讯作者：
Michaelides, Angelos