A Theoretical Benchmark of the Geometric and Optical Properties for 3d Transition Metal Nanoclusters via Density Functional Theory

Understanding structure–property relationships
in atomically
precise metal nanoclusters is vital in finding selective and tunable
catalysts. In this study, density functional theory (DFT) was used
to benchmark seven exchange correlation functionals at different basis
sets for 17 atomically precise nanoclusters against experimentally
determined geometries, band gaps, and optical gaps. The set contains
both monometallic and bimetallic clusters that possess at least two
types of 3d transition metals (specifically, Cu, Ni, Fe, or Co). The
benchmark highlights that PBE0 is a good functional to use regardless
of the basis set, and Minnesota functionals do well with respect to
specific metals. Further, while long-range corrected functionals overestimate
band and optical gaps, they model absorption features better than
the other considered functionals. The study additionally looks at
the photoinduced hydrogen evolution reaction (HER) and the CO2 reduction mechanism on nanoclusters reported from the literature.