First-principles-based optimization of electronic structures for bimetallic nanoparticles

Abstract Based on the first-principle calculation combined with cluster expansion technique and Monte Carlo statistical simulation, we propose an optimization of local electronic structure in bimetallic nanoparticles. We apply the proposed optimization to Pt-Rh nanoparticles, and find that Pt d -band center can be quantitatively described by finite set of basis functions in terms of atomic arrangements. Consequently, electronic structures of Pt d -band at specific site can be reasonably controlled by changing surrounding atomic arrangements, which enables systematic changes in molecular adsorption energy.