Resolving Contradictory Estimates of Band Gaps of Bulk PdSe$_2$: A Wannier-Localized Optimally-Tuned Screened Range-Separated Hybrid Density Functional Theory Study (2501.15334v1)

Abstract: Palladium diselenide (PdSe$_2$) -- a layered van der Waals material -- is attracting significant attention for optoelectronics due to the wide tunability of its band gap from the infrared through the visible range as a function of the number of layers. However, there continues to be disagreement over the precise nature and value of the optical band gap of bulk PdSe$_2$, owing to the rather small value of this gap that complicates experimental measurements and their interpretation. Here, we design and employ a Wannier-localized optimally-tuned screened range-separated hybrid (WOT-SRSH) functional to investigate the electronic bandstructures and optical absorption spectra of bulk and monolayer PdSe$_2$. In particular, we account carefully for the finite exciton center-of-mass momentum within a time-dependent WOT-SRSH framework to calculate the \emph{indirect} optical gap and absorption onset accurately. Our results agree well with the best available photoconductivity measurements, as well as with state-of-the-art many-body perturbation theory calculations, confirming that bulk PdSe$_2$ has an optical gap in the mid-infrared (upper-bound of 0.44 eV). More generally, this work further bolsters the utility of the WOT-SRSH approach for predictive modeling of layered semiconductors.