Influence of back donation effects on the structure of ZnO nanoclusters

The structure and properties of ZnO quantum dots is a very popular and rapidly growing field of research for which accurate quantum calculations are challenging to perform. Since the dependence between system size and wall time scales nonlinearly, certain compromises have to be made. A particularly important limiting factor is the size of the basis used, this is especially the case if accurate large calculations are to be carried out. In our work, we discovered that an important O(2p)‐>Zn(4p) back donation, which greatly influences the strength of the ZnO bond, can be reproduced only if diffuse functions are added to the basis set. We further tested the basis dependence for the magic‐sized wurtzite nanophase ZnO clusters which were previously shown to be able to accurately reproduce the magnetically doped II‐IV Q‐dots. In this work, we outline the minimal basis sets required to properly describe ZnO bonds in a nanocluster. It was demonstrated that the rock salt nanophase is incorrectly stabilized if a basis set does not contain sufficiently diffuse functions while the correct wurtzite phase is stabilized when diffuse functions are added. This tendency, similar to that in the ZnO dimer case, was shown to stem from the incorrect lack of Zn(4p) electron density in calculations when using the diffuse‐free basis set.