Computational Characterization of the Intermixing of Iron Triade (Fe, Co, and Ni) Surfaces and Sub-nanometric Clusters with Atomic Gold

[Image: see text] Dispersion-corrected density functional theory (DFT-D3) is applied to model iron triade (Fe, Co, and Ni) surfaces upon exchange of surface atoms with atomic gold. One first goal is to analyze the contact problem at the triade surface–Au interface and to correlate our findings with recent observations on iron triade nanoparticles (with diameters of around 5 nm) passivated by a few layers of gold. For this purpose, we analyze: (1) the energies of substitution; (2) the restructuring of the iron triade surfaces upon the atomic exchange; (3) the density of the orbitals bearing the largest projection on d(Au) atomic orbitals and, particularly, their overlap with orbitals from neighboring atoms of the triade surfaces; (4) the modification of the electronic density of states; and (5) the redistribution of the electronic density upon intermixing of Au and triade atoms. Inspite of the similarities between Ni, Co, and Fe in the condensed phase, significant differences are found in the features characterizing the exchange process. In particular, we find a better integration of the Au atom on the substitutional site of the Ni(001) surface than on those of the Fe(001) and Co(001) surfaces. This is in agreement with the fact that the electronic density of states is almost indistinguishable before and after Ni–Au intermixing. This outcome is correlated with the experimental observation on the allowing transition of Ni–Au core–shell nanoparticles before reaching the melting temperature. Our second objective is to explore the Au–triade atom intermixing process in sub-nanometric clusters, finding that it is energetically more favored than at solid surfaces yet endothermic at 0 K. This feature is explained as the result of the structural fluxionality characterizing clusters at the sub-nanometer scale. Entropy contributions make mixed Au–Ni clusters more stable than the unmixed counterpart already at 650 K while unmixed Co clusters remain energetically more favored up to 1295 K and iron clusters are predicted to be stable against intermixing over the experimentally relevant range of temperatures (up to 1100 °C). Remarkably, the net charge donated from the three triade atoms to atomic gold upon intermixing is similar in triade sub-nanometeric clusters and at extended triade surfaces. Gold clusters are prone to host Fe, Co, and Ni atoms at the center of their structures and the exchange process is predicted to be exothermic at 0 K even for a small cluster made of 13 atoms. More generally, our work highlights the importance of the polarity of the chemical bond between unlike metal atoms in alloys.