The description of electronic properties of low bandgap molecular system is often performed by using density functional theory (DFT) and time dependent (TD) DFT calculations with the optimally tuned range-separated hybrid (OT-RSH) functional, as it contains the necessary ingredients to reliably predict charge transfer excitations. However, the range separating parameter (ω) is system-dependent and its optimization, including the chemical environment, is intricate. Refaely-Abramson et al. demonstrated that the gap renormalization in molecular crystals, a ground state property, can be represented by an OT-RSH functional screened by ɛstatic [Phys. Rev. B 88, 081204(R) (2013)], the zero frequency scalar dielectric constant. In this study, we propose the use of an OT-RSH functional screened by the scalar dielectric constant in the high frequency limit (OT-sRSH), ɛ∞, an appropriate constraint for vertical ionization energies or excitations in a dielectric environment. We have performed calculations for S,N-heteroacene derivatives in tetrahydrofuran and dichloromethane. The “unscreened” OT-RSH functional tends to underestimate experimental ionization potentials (IPs) and optical gaps (Egs) by up to 1.5 and 0.5 eV, respectively. In contrast, OT-sRSH functional calculations underestimate IPs and Egs by only 0.4 and 0.2 eV. We also compared the OT-sRSH results to explicitly solvated OT-RSH functional calculations for oligothiophenes in dioxane, benzene in ammonia, and methylene blue in water. We observe that both the approaches perform similarly for weakly interacting intermolecular systems and deviate for solvent–solute interacting systems, as expected. In conclusion, the OT-sRSH functional can describe molecular systems with environmental polarization effects accurately, a step toward describing realistic molecular systems.
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As previously discussed, we note that it is difficult to conceive an experiment to measure “vertical IPs” in a solution or any medium, with few exceptions as the Liquid-Jet Photoelectron Spectroscopy.70,80 Thus, we regard the term “theoretical” vertical IP as the offset energy to eject one electron from the molecular system while only the electronic density reacts to the new configuration. Our concept of vertical IP and the experimental adiabatic IP approximate when the molecules are rigid and the medium is apolar such the reorganization energy is small compared to the ionization energies.
