Is a Highly Ionic Material Still Ionic as a Nanoparticle?

Abstract The evolution of ionicity with size in highly ionic nanoparticles is investigated in small sesquioxide clusters. Representative clusters (Y₂O₃)_N (N < 50) are theoretically analyzed by first‐principle calculations within the density functional theory within the local‐density approximation (DFT‐LDA) framework and compared to experimental results obtained in an ultrahigh vacuum environment. By studying the structural relaxation and the electronic density of states as a function of size, the respective roles of ionicity and covalency are elucidated. For compounds as ionic as rare earth sesquioxides, the highly ionic bond essentially governs and preserves the crystalline structure. Particular attention is paid to the mechanism responsible for the surface relaxation. The role of the ions at the corners and edges appears prominent, especially in reducing the dipole carried by the particles. Eventually, contrary to the observations and computations concerning ionic surfaces, the mean ionicity remains constant as the size is reduced. It emphasizes that the description of highly ionic nanoparticles cannot be directly inferred from knowledge regarding the ionic surface reconstruction.