On the anti-compensation effect?

The kinetic compensation effect (KCE) refers to an observed systematic variation in the apparent magnitudes of the Arrhenius parameters, the energy of activation E_a, and the preexponential factor ν, as a response to perturbations. The extracted parameters tend to exhibit a strong positive linear correlation. This is attributed to enthalpic and entropic contributions changing in the same direction. However, when these contributions change in the opposite direction, a negative linear correlation is expected, the anti-compensation effect.

As part of a systematic study on the KCE, we use kinetic Monte Carlo simulations to study the effects of repulsive lateral interactions on the Arrhenius parameters during the thermal desorption of quasi spherical adsorbates from two dimensional ordered and disordered surfaces. The purpose is to observe if an anti compensation is observed, as well as to study the transient behavior of the Arrhenius parameters when different 'experimental' parameters have been altered, since previous results show the occurrence of partial compensation, despite a strong linear correlation between E_a and ln ν. We expect our results to help advance the understanding of the microscopic origins of compensation and possible anti compensation effects, in our system of study but also in other fields where these effects have been reported.