Technische Universität Berlin, Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Straße des 17. Juni 135, D-10623, Berlin, Germany.
J Chem Theory Comput. 2023 Jun 13;19(11):3146-3158. doi: 10.1021/acs.jctc.3c00173. Epub 2023 May 19.
The optimal tuning (OT) of range-separated hybrid (RSH) functionals has been proposed as the currently most accurate DFT-based way to compute the relevant quantities required for charge-transfer processes in organic chromophores used in organic photovoltaics and related fields. The main drawback of OT-RSHs is that the system-specific tuning of the range-separation parameter is not size-consistent. It therefore also lacks transferability, e.g., when considering processes involving orbitals not involved in the tuning or for reactions between different chromophores. Here we show that the recently reported ωLH22t range-separated local hybrid functional provides ionization energies, electron affinities, and fundamental gaps on par with OT-RSH treatments, approaching the quality of GW results, without any need for system-specific tuning. This holds from relevant organic chromophores of varying sizes all the way to atomic electron affinities. ωLH22t also gives excellent outer-valence quasiparticle spectra and is a generally accurate functional for both main-group and transition-metal energetics, as well as for a variety of excitation types. Range-separated local hybrid functionals are suggested as promising new quantum-chemical tools in molecular electronics.
最优调谐（OT）的离域混合（RSH）泛函被提议为目前最准确的基于密度泛函理论的方法，用于计算有机光伏和相关领域中用于电荷转移过程的相关数量。OT-RSH 的主要缺点是，范围分离参数的系统特定调谐不是大小一致的。因此，它也缺乏可转移性，例如，当涉及到不参与调谐的轨道或不同发色团之间的反应时。在这里，我们表明最近报道的 ωLH22t 离域局部混合泛函提供的电离能、电子亲合能和基本能隙与 OT-RSH 处理相当，接近 GW 结果的质量，而无需进行特定系统的调谐。这适用于各种大小的相关有机发色团，一直到原子电子亲合能。ωLH22t 还给出了出色的外价准粒子谱，并且是一种对于主族和过渡金属能学以及各种激发类型都非常准确的泛函。离域局部混合泛函被建议作为分子电子学中很有前途的新量子化学工具。
