支持型分子开关中的多维氢隧道效应：表面相互作用的作用
Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions
摘要：
支撑分子开关结构中氢转移反应的核隧穿交叉温度（$T_c$）可以接近室温。这就要求在计算反应速率时，即使在高温下也要考虑核量子效应（NQE）。然而，NQE的标准计算依赖于参数化的降维模型，在这些环境中很快变得不足。在这封信中，我们研究了基于卟啉分子吸附在金属表面的范式分子开关的全维计算，结合密度泛函理论的电子和半经典环聚合物瞬子近似的核。我们表明，双分子内氢转移（DHT）率可以提高数量级，由于深隧穿制度的表面波动。我们还解释了起源的阿克里乌斯温度依赖的速率低于$T_c$，为什么这种依赖性在不同的表面不同。我们提出了一个简单的模型来合理化不同fcc [110]表面的DHT速率的温度依赖性。
英文摘要：
The nuclear tunneling crossover temperature ($T_c$) of hydrogen transfer reactions in supported molecular-switch architectures can lie close to room temperature. This calls for the inclusion of nuclear quantum effects (NQE) in the calculation of reaction rates even at high temperatures. However, standard computations of NQE relying on parametrized dimensionality-reduced models, quickly become inadequate in these environments. In this letter, we study the paradigmatic molecular switch based on porphycene molecules adsorbed on metallic surfaces with full-dimensional calculations that combine density-functional theory for the electrons with the semi-classical ring-polymer instanton approximation for the nuclei. We show that the double intramolecular hydrogen transfer (DHT) rate can be enhanced by orders of magnitude due to surface fluctuations in the deep tunneling regime. We also explain the origin of an Arrhenius temperature-dependence of the rate below $T_c$ and why this dependence differs at different surfaces. We propose a simple model to rationalize the temperature dependence of DHT rates spanning diverse fcc [110] surfaces.
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