Equilibrium and kinetic isotope effects in heterogeneous catalysis: A density functional theory perspective
Benjamin W. J. Chen
Abstract
Isotopes are indispensable tools for elucidating catalytic reaction mechanisms. Yet, computational isotopic studies in heterogeneous catalysis remain scarce, especially when compared with other subfields of chemistry. In this review, we discuss isotope effects from a computational viewpoint, focusing specifically on heterogeneous catalysts. First, we review methods for predicting kinetic and equilibrium isotope effects of individual elementary steps, as well as for simulating the apparent kinetic isotope effects of multistep reactions. Second, we discuss the influence of the often-neglected catalytic environment, such as the presence of different binding sites and non-zero adsorbate coverages. Third, we present case studies illustrating possible pitfalls when performing isotope studies and how computations can help avoid them. Finally, we share our outlook on possible future applications of isotope effects. Throughout the review, we highlight the promising synergies that can be gained by combining experiments and computations.