Enhanced sampling study of the methylation of ethene, propene and trans-2-butene.

For optimal catalyst design, a thorough understanding of elementary reaction steps on a molecular level is crucial. Therefore, the quest to attain chemical accuracy (4 kJ/mol for the energy barriers and one order of magnitude for the pre-exponential factors) using ab initio techniques is of utmost importance. A recent contribution is done by Piccini et al. by presenting a divide-and-conquer strategy, emphasizing on the importance of the anharmonic behavior of the system. Therefore, we would like to simulate the same reactions using umbrella sampling, since this technique is able to directly account for the dynamic behavior of the system enabling us to aid in the quest for chemical accuracy with ab initio simulations.