A central problem in multicomponent lattice systems is to systematically quantify multi-point ordering. Ordering in such systems is often described in terms of pairs, even though this is not sufficient when three-point and higher-order interactions are included in the Hamiltonian. Current models and parameters for multi-point ordering are often only applicable for very specific cases and/or require approximating a subset of correlated occupational variables on a lattice as being uncorrelated. In this work, a cluster order parameter (ClstOP) is introduced to systematically quantify arbitrary multi-point ordering motifs in substitutional systems through direct calculations of normalized cluster probabilities. These parameters can describe multi-point chemical ordering in crystal systems with multiple sublattices, multiple components, and systems with reduced symmetry. These are defined within and applied to quantify four-point chemical ordering motifs in platinum/palladium alloy nanoparticles that are practical interest to the synthesis of catalytic nanocages. Impacts of chemical ordering on alloy nanocage stability are discussed. It is demonstrated that approximating 4-point probabilities from superpositions of lower order pair probabilities is not sufficient in cases where 3 and 4-body terms are included in the energy expression. Conclusions about the formation mechanisms of nanocages may change significantly when using common pair approximations.
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