Abstract
The recently introduced four atom cluster model is used to obtain higher order conditional probabilities that describe the atomic correlations in some molten binary alloys. Although the excess free energy of mixing for all the systems studied are almost symmetrical about the equiatomic composition, most other thermodynamic quantities are not and thus, the study enables us to explain the subtle differences in their physical characteristics required to describe the mechanism of the observed strong heterocoordination in Au–Zn or homocoordination in Cu–Ni within the same framework. More importantly, we obtain all calculated quantities for the whole concentration range thus complimenting experimental evidence.
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