柔性吸附分子偶氮苯在Ag（111）表面的热涨落和电子涨落
Thermal and electronic fluctuations of flexible adsorbed molecules: Azobenzene on Ag(111)
摘要：
我们以Ag（111）表面上的分子开关偶氮苯C $_{12}$ H $_{10}$ N $_{2}$为例，研究了影响柔性吸附物在表面上有限温度吸附性质的热和电子集体涨落.使用第一性原理分子动力学模拟，我们得到的吸附自由能，准确地占熵的贡献，而列入多体分散相互作用占电子相关性，管理吸附结合。我们发现吸附质的性质是强烈的熵驱动，可以判断的动力学分子解吸前因子10 $^{24}$ s $^{-1}$，大大超过以前报道的估计。我们将这种效应与结构和电子观测量的相当大的波动联系起来。我们的计算程序升温脱附测量的比较表明，有限温度效应发挥主导作用的柔性分子与极化表面接触，最近开发的第一性原理方法提供了一个最佳的工具，以揭示新的集体行为在这样的复杂系统。
英文摘要：
We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C$_{12}$H$_{10}$N$_{2}$ on the Ag(111) surface. Using first-principles molecular dynamics simulations we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy-driven, as can be judged by a kinetic molecular desorption prefactor of 10$^{24}$ s$^{-1}$ that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. Comparison of our calculations to temperature-programmed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems.
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