An Automated Approach for Developing Graph-Theoretical Cluster Expansions of the Total Energy of Adsorbed Layers

摘要

The accurate description of the total energy of adsorbate layers is crucial for the understanding of chemistry at interfaces. For catalysis applications in particular, adsorbate-adsorbate lateral interactions have been shown to significantly affect activation energies of reactions, thereby shaping experimentally observed trends. [1,2] Modelling the interactions of atomic adsorbates has traditionally been achieved using effective Ising-type Hamiltonians [3], whereby a set of spin-like values is attributed to the layer’s lattice points describing the occupancy of the corresponding catalytic sites (vacant occupied by a species). Pairwise additive adsorbate-adsorbate lateral interactions in this model are captured by appropriate coupling constants.