A systematic study of the kinetic compensation effect in thermal desorption

The kinetic compensation effect (KCE) is an observed systematic variation in the apparent magnitudes of the Arrhenius parameters the energy of activation E_a and the preexponential factor ν of many activated processes as a response to perturbations. The variations often result in a linear correlation, which is often explained as being a consequence of a mutual offsetting between E_a and ln ν. We conduct a systematic study on the kinetic compensation effect through kinetic Monte Carlo simulations, to study the effects on the rates when an 'experimental parameter' has been altered during the thermal desorption of quasi spherical adsorbates from different surface configurations.By numerically calculating the activation energy, while the following parameters are varied: lateral interaction strength, surface morphology, concentration of an additive, in addition to studying the effects of repulsive interactions (anti compensation effect). Our results show a mutual variation which yields a partial compensation effect, as opposed to a complete mutual offsetting. We attempt to understand the transient behavior of the parameters to provide a picture of the microscopic origins of the KCE in this system, and perhaps to help understand its origins in other systems.