论文标题
弱键界面处的量子核：RH上的环己烷的情况（111）
Quantum Nuclei at Weakly Bonded Interfaces: The Case of Cyclohexane on Rh(111)
论文作者
论文摘要
接口的电子特性可以取决于它们的同位素构成。一种已知的情况是在RH（111）上的环己烷物理学的情况，其中已经测量了工作函数变化和解吸能的同位素效应。这些效应只能通过包括核量子效应（NQE）在内的计算来捕获。在本文中，该界面采用了包含分散的密度功能理论，该理论与NQE的准谐波（QH）近似结合，以及完全无谐的admonic abiboloin abiboloin rot in libinious rot径静物积分分子动力学（PIMD）。 QH近似能够捕获氘代环己烷具有较小的吸附能，并且与RH（111）表面相比，与同位素学相比，在距离RH（111）表面较远约0.01，这可以与工作函数变化的同位素效应相关。对QH近似有效性的研究依赖于PIMD模拟，得出的结论是，尽管该界面受到分子层中的Anharmonic量子波动的高度影响，但在分析低温下同位素效应时，这些非谐作者在分子效应时起较小的作用。然而，Anharmonic量子波动会导致分子层和RH之间的距离增加（111），因此，较小的总体工作函数变化以及轨道杂交的复杂变化。
The electronic properties of interfaces can depend on their isotopic constitution. One known case is that of cyclohexane physisorbed on Rh(111), in which isotope effects have been measured on the work function change and desorption energies. These effects can only be captured by calculations including nuclear quantum effects (NQE). In this paper, this interface is addressed employing dispersion-inclusive density-functional theory coupled to a quasi-harmonic (QH) approximation for NQE, as well as to fully anharmonic ab initio path integral molecular dynamics (PIMD). The QH approximation is able to capture that deuterated cyclohexane has a smaller adsorption energy and lies about 0.01 A farther from the Rh(111) surface than its isotopologue, which can be correlated to the isotope effect in the work function change. An investigation of the validity of the QH approximation relying on PIMD simulations, leads to the conclusion that although this interface is highly impacted by anharmonic quantum fluctuations in the molecular layer and at bonding sites, these anharmonic contributions play a minor role when analysing isotope effects at low temperatures. Nevertheless, anharmonic quantum fluctuations cause an increase in the distance between the molecular layer and Rh(111), a consequent smaller overall work function change, and intricate changes in orbital hybridization.
