DFT calculations of metal-organic I-III-VI semiconductor clusters: Benchmark of exchange-correlation functionals and localized basis sets

Abstract

The primary objective of this work was to find the numerical methods suitable for DFT calculations of ternary I-III-VI semiconductor quantum dots emerging as new functional materials which demonstrate an increasing need to comprehend their complex physicochemical properties. The benchmarking analysis of 8 exchange-correlation functionals and 11 basis sets including all-electron and effective core potential ones was performed. Four metal-organic molecules, widely used as a single-precursor in the synthesis of A-In-X2 semiconductor quantum dots (A = Cu, Ag; X = S, Se) were considered as simple representatives of ternary semiconductor quantum dots. The geometrical parameters of the optimized structures were compared to the X-ray diffraction data. The hybrid PBE0 and B3PW91 functionals were found to be the best performing methods especially when connected with cc-PVDZ or Def2-SVP basis sets. The methods widely used in the previous calculations of II-VI semiconductor quantum dots, namely B3LYP functional and LANL2DZ or SBKJC basis sets, in this case resulted in lower agreement with the experimental data.