金属支撑分子开关的计算设计：光和电子诱导偶氮苯异构化过程中的瞬态离子形成
Computational design of metal-supported molecular switches: Transient ion formation during light- and electron-induced isomerisation of azobenzene
摘要：
在分子纳米技术中，单个分子被设想为电子器件的基本构建块。这样的器件对于有机光致发光、数据存储和机敏材料可能是特别感兴趣的。然而，分子官能团通常在与导电载体接触时被淬灭。通过分子功能化和改变底物的基于试错的解耦策略在许多情况下被证明会产生不可预测的结果。可以理解的第一性原理模拟的帮助下，吸附物-基板的相互作用，支配的功能。采用色散校正的密度泛函理论和线性展开的δ自洽场密度泛函理论，研究了偶氮苯吸附在铜、银和金单晶（111）面上的电子结构，并分析了吸附后开关功能丧失或保留的主要原因.基于其瞬态分子离子的激发态势能景观，评估了偶氮苯在Au（111）上的功能化衍生物和偶氮苯在Ag（111）和Au（111）上的光致开关能力，这些瞬态分子离子被认为是实验观察到的异构化反应的主要中间体。我们提供了一个合理化的实验观察到的功能或缺乏其连接到金属表面相互作用的基础化学，并提供了深入了解复杂的光驱动反应在金属表面的一般设计策略。
英文摘要：
In molecular nanotechnology, a single molecule is envisioned to act as the basic building block of electronic devices. Such devices may be of special interest for organic photovoltaics, data storage, and smart materials. However, more often than not the molecular function is quenched upon contact with a conducting support. Trial-and-error-based decoupling strategies via molecular functionalisation and change of substrate have in many instances proven to yield unpredictable results. The adsorbate-substrate interactions that govern the function can be understood with the help of first-principles simulation. Employing dispersion-corrected Density-Functional Theory (DFT) and linear expansion Delta-Self-Consistent-Field DFT, the electronic structure of a prototypical surface-adsorbed functional molecule, namely azobenzene adsorbed to (111) single crystal facets of copper, silver and gold, is investigated and the main reasons for the loss or survival of the switching function upon adsorption are identified. The light-induced switching ability of a functionalised derivative of azobenzene on Au(111) and azobenzene on Ag(111) and Au(111) is assessed based on the excited-state potential energy landscapes of their transient molecular ions, which are believed to be the main intermediates of the experimentally observed isomerisation reaction. We provide a rationalisation of the experimentally observed function or lack thereof that connects to the underlying chemistry of the metal-surface interaction and provides insights into general design strategies for complex light-driven reactions at metal surfaces.
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