We compute the electronic structure and optical excitation energies of metal-free and transition metal phthalocyanines (H2Pc and MPc for M = Fe, Co, Ni, Cu, Zn, Mg) using density functionaltheory with optimally-tuned range-separated hybrid functionals (OT-RSH).We show that the OT-RSH approach provides photoemission spectra in quantitative agreement with experimentsas well as optical band gaps within 10% of their experimental values, capturing the interplay of localized d-states and delocalized pi-pi* states for these organometallic compounds. We examine the tunability of MPcs and H2Pc through fluorination, resulting in quasi-rigid shifts of the molecular orbital energies by up to about 0.7 eV. Our comprehensive dataset provides a new computational benchmark for phthalocyanines molecules, significantly improving upon other density-functional-theory-based approaches.

中文翻译：

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金属酞菁，MPc（M = Fe，Co，Ni，Cu，Zn，Mg）和氟化MPc的电子结构

我们使用密度泛函理论和最佳调整范围分离混合函数（OT）来计算无金属和过渡金属酞菁（H2Pc和MPc对于M = Fe，Co，Ni，Cu，Zn，Mg）的电子结构和光激发能-RSH）。我们证明了OT-RSH方法可提供与实验定量一致的光发射光谱，以及在其实验值的10％以内的光学带隙，从而捕获了这些d态和pi-pi *态的相互作用有机金属化合物。我们检查了通过氟化作用产生的MPcs和H2Pc的可调谐性，导致分子轨道能量的准刚性位移高达约0.7 eV。我们全面的数据集为酞菁分子提供了新的计算基准，