论文标题
热载体转移穿过纳米粒子 - 分子连接：轨道杂交和水平比对的重要性
Hot-carrier transfer across a nanoparticle-molecule junction: The importance of orbital hybridization and level alignment
论文作者
论文摘要
虽然直接热载体转移可以增加照片催化活性，但很难辨别实验并与其他几种机制竞争。为了阐明这些方面，我们从等离子体纳米颗粒和CO分子之间的界面中的第一原理热载体产生建模。热电子转移概率在非单调的纳米粒子 - 分子距离上取决于远距离，并且可以在化学吸附区域内有效。另一方面，热孔传输仅限于较短的距离。这些观察结果可以通过分子和纳米颗粒状态之间的能量比对以及激发频率来解释。分子轨道的杂交是这些系统中热载体转移的关键预测指标，强调需要包括基态杂交以进行准确预测的效果。最后，我们显示了热载体分布对激发能的非平凡依赖性，在优化光催化系统时可以利用这些分布。
While direct hot-carrier transfer can increase photo-catalytic activity, it is difficult to discern experimentally and competes with several other mechanisms. To shed light on these aspects, here, we model from first principles hot-carrier generation across the interface between plasmonic nanoparticles and a CO molecule. The hot-electron transfer probability depends non-monotonically on the nanoparticle-molecule distance and can be effective at long distances, well outside the region of chemisorption; hot-hole transfer on the other hand is limited to shorter distances. These observations can be explained by the energetic alignment between molecular and nanoparticle states as well as the excitation frequency. The hybridization of the molecular orbitals is the key predictor for hot-carrier transfer in these systems, emphasizing the need to include the effects of ground state hybridization for accurate predictions. Finally, we show a non-trivial dependence of the hot-carrier distribution on the excitation energy, which could be exploited when optimizing photo-catalytic systems.
