Fundamental and excitation gaps in molecules of relevance for organic photovoltaics from an optimally tuned range-separated hybrid functional

By S. Refaely-Abramson, Roi Baer, Leeor Kronik. 2011

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The fundamental and optical gaps of relevant molecular systems are of primary importance for organic-based photovoltaics. Unfortunately, whereas optical gaps are accessible with time-dependent density functional theory (DFT), the highest-occupied – lowest-unoccupied eigenvalue gaps resulting from DFT calculations with semi-local or hybrid functionals routinely and severely underestimate the fundamental gaps of gas-phase organic molecules. Here, we show that a range-separated hybrid functional, optimally tuned so as to obey Koopmans’ theorem, provides fundamental gaps that are very close to benchmark results obtained from many-body perturbation theory in the GW approximation. We then show that using this functional does not compromise the possibility of obtaining reliable optical gaps from time-dependent DFT. We therefore suggest optimally tuned range-separated hybrid functionals as a practical and accurate tool for DFT-based predictions of photovoltaically relevant and other molecular systems.

Subfields: Atomic and Molecular Physics, and Optics, Electrical and Electronic Engineering

View Paper: https://www.semanticscholar.org/paper/a0175dc2aa7e1df56eeea16cedc9e9021e0028d2