Calibrating the Extended Hückel Method to Quantitatively Screen the Electronic Properties of Materials

The extended Hückel (eH) tight-binding method has historically been prized for its computational ease and intuitive chemical clarity. However, its lack of quantitative predictiveness has prevented the eH method from being used as a tool for rapidly screening materials for desired electronic properties. In this work, we demonstrate that when eH input parameters are calibrated using density functional theory (DFT) calculations of carefully chosen sets of simple crystals, the eH parameters retain most of their quantitative accuracy when transferred to more complex, structurally related phases. Using solar-energy-relevant semiconductors and insulators in the Sr–Ti–O family as a case study, we show that calibrated eH parameters can match the features of DFT band structures within about two tenths of an eV, at a tiny fraction of the computational cost of DFT.