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$G_0W_0$ calculations for predicting vertical ionization potentials (IPs) andelectron affinities of molecules and clusters are known to show a significantdependence on the density functional theory (DFT) starting point. A number ofnon-empirical procedures to find an optimal starting point have been proposed,typically based on tuning the amount of HF exchange in the underlying hybridfunctional specifically for the system at hand. For the case of$\pi$-conjugated molecular chains, these approaches lead to a significantlydifferent amount of HF exchange for different oligomer sizes. In this study, weanalyze if and how strongly this size dependence affects the ability ofnon-empirical tuning approaches to predict accurate IPs for $\pi$-conjugatedmolecular chains of increasing chain length. To this end, we employ threedifferent non-empirical tuning procedures for the $G_0W_0$ starting point tocalculate the IP of polyene oligomers up to 22 repeat units and compare theresults to highly accurate coupled-cluster calculations. We find that, despiteits size dependence, using an IP-tuned hybrid functional as a starting pointfor $G_0W_0$ yields excellent agreement with the reference data for all chainlengths.

Size-dependence of non-empirically tuned DFT starting points for $G_0W_0$ applied to ${\pi}$-conjugated molecular chains