物理脱附中动力学补偿效应的失效
Breakdown of Kinetic Compensation Effect in Physical Desorption
摘要：
动力学补偿效应（KCE）是在许多科学领域中观察到的，是作为对扰动的响应的阿耳忒修斯参数$E_a$（活化能）和$ν$（指前因子）的表观幅度的系统变化。如果在一系列密切相关的活化过程中，这些参数表现出很强的线性相关性，则预期将出现等动力学关系，然后在共同的补偿温度$T_c$下，速率$k$变得相同。这两种现象的真实性仍然存在争议，因为它们没有得到明确的证明，它们的物理起源仍然知之甚少。使用动力学蒙特卡罗模拟的模型接口，我们探讨如何网站和吸附相互作用的影响，在一个典型的解吸过程中的Arrhenius参数。我们发现，他们的瞬态变化导致净部分补偿，由于前因子的变化不足以完全抵消那些在$E_a$，无论是在图中表现出高度的线性和弯曲的非Arrhenius图。此外，所观察到的等速关系的出现是由于过渡到一个非相互作用的制度，而不是由于$E_a$和$\lnν$之间的补偿。我们希望我们的研究结果提供了一个更深入的了解微观事件，起源补偿效应和等速在我们的系统中的关系，并在其他领域，这些影响已被报道。
英文摘要：
The kinetic compensation effect (KCE), observed in many fields of science, is the systematic variation in the apparent magnitudes of the Arrhenius parameters $E_a$, the energy of activation, and $ν$, the preexponential factor, as a response to perturbations. If, in a series of closely related activated processes, these parameters exhibit a strong linear correlation, it is expected that an isokinetic relation will occur, then the rates $k$ become the same at a common compensation temperature $T_c$. The reality of these two phenomena continues to be debated as they have not been explicitly demonstrated and their physical origins remain poorly understood. Using kinetic Monte Carlo simulations on a model interface, we explore how site and adsorbate interactions influence the Arrhenius parameters during a typical desorption process. We find that their transient variations result in a net partial compensation, due to the variations in the prefactor not being large enough to completely offset those in $E_a$, both in plots that exhibit a high degree of linearity and in curved non-Arrhenius plots. In addition, the observed isokinetic relation arises due to a transition to a non-interacting regime, and not due to compensation between $E_a$ and $\lnν$. We expect our results to provide a deeper insight into the microscopic events that originate compensation effects and isokinetic relations in our system, and in other fields where these effects have been reported.
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