Exchange Functionals and Basis Sets for Density Functional Theory Studies of Water Splitting on Selected ZnO Nanocluster Catalysts

[Image: see text] In this communication, we use density functional theory (DFT) to study the structural (geometry) and electronic properties (vertical detachment energy and electron affinity) of ZnO monomers and dimers that can be used to form ZnO clusters of different sizes, with a view to adapting one or more of them as catalysts or photocatalysts, standing alone or on suitable substrates like graphene, to split water. We also investigate different pairs of exchange functionals and basis sets to optimize their choice in our DFT calculations and to compare the singlet–triplet energy gaps of small ZnO clusters of different sizes to select an optimal cluster size for water splitting. We find that the B3LYP/DGDZVP2 exchange functional/basis set is a reliable combination for use with DFT to calculate the geometry and electronic properties of small ZnO nanoclusters from among several other combinations of exchange functionals and basis sets. Comparisons of the singlet–triplet energy gaps show that the trimer (ZnO)(3) has an energy gap of 58.66 k cal/mol. which is approximately equal to the energy of a visible photon at a wavelength of 500 nm, and a HOMO–LUMO gap of 4.4 eV, making it a suitable choice of photocatalyst for the oxidation of water from among six (ZnO)(n) nanoclusters of monomers, with n ranging from 1 to 6. We used this exchange functional/basis set to study the structural and energetic details of hydration and hydrolysis of water absorbed on the (ZnO)(3) nanocatalyst and calculated the corresponding potential energy profiles to identify three sets of singlet–triplet pathways for water splitting. Detailed study of a pathway showed that oxygen is produced after hydrogen, and the rate-determining step is the formation of hydrogen.