Exceptional Spatial Variation of Charge Injection Energies on Plasmonic Surfaces
Exceptional Spatial Variation of Charge Injection Energies on Plasmonic Surfaces
复制标题
等离子表面电荷注入能量的异常空间变化
DOI：
10.1021/acs.jpclett.3c02223
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Vlcek, Vojtech
中科院分区：
文献类型：
--
作者：
Lei, Xiaohe;Canestraight, Annabelle;Vlcek, Vojtech
电荷注入金属界面上的分子是许多光活化反应中的关键步骤。我们采用多体微扰理论计算了CO2分子在含有103，000个电子的Au纳米颗粒上的空穴和电子注入能，并与理想化的无限表面的结果进行了比较.我们证明了一个令人惊讶的大变化的注入能垒取决于表面上的精确分子位置。多个“热点”，其特征在于低能量势垒，出现由于等离子体耦合和分子和基板之间的杂交程度之间的竞争。纳米颗粒表面吸附物的电荷注入势垒从小平面边缘到小平面中心逐渐减小。这一发现与其中纳米颗粒边缘上的电场增强被认为是最关键因素的典型图片形成对比。
Charge injection into a molecule on a metallic interface is a key step in many photoactivated reactions. We employ the many-body perturbation theory and compute the hole and electron injection energies for CO2molecule on an Au nanoparticle with ∼3,000 electrons and compare it to results for idealized infinite surfaces. We demonstrate a surprisingly large variation of the injection energy barrier depending on the precise molecular position on the surface. Multiple “hot spots,” characterized by low energy barriers, arise due to the competition between the plasmonic coupling and the degree of hybridization between the molecule and the substrate. The charge injection barrier to the adsorbate on the nanoparticle surface decreases from the facet edge to the facet center. This finding contrasts with the typical picture in which the electric field enhancement on the nanoparticle edges is considered the most critical factor.