Department of Physical Chemistry and Materials Science, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3., H-1111 Budapest, Hungary.
J Chem Theory Comput. 2022 Mar 8;18(3):1646-1662. doi: 10.1021/acs.jctc.1c01307. Epub 2022 Feb 24.
The performance of the most recent density functionals is assessed for charge-transfer (CT) excitations using comprehensive intra- and intermolecular CT benchmark sets with high-quality reference values. For this comparison, the state-of-the-art range-separated (RS) and long-range-corrected (LC) double hybrid (DH) approaches are selected, and global DH and LC hybrid functionals are also inspected. The correct long-range behavior of the exchange-correlation (XC) energy is extensively studied, and various CT descriptors are compared as well. Our results show that the most robust performance is attained by RS-PBE-P86/SOS-ADC(2), as it is suitable to describe both types of CT excitations with outstanding accuracy. Furthermore, concerning the intramolecular transitions, unexpectedly excellent results are obtained for most of the global DHs, but their limitations are also demonstrated for bimolecular complexes. Despite the outstanding performance of the LC-DH methods for common intramolecular excitations, serious deficiencies are pointed out for intermolecular CT transitions, and the wrong long-range behavior of the XC energy is revealed. The application of LC hybrids to such transitions is not recommended in any respect.
采用具有高质量参考值的综合分子内和分子间电荷转移 (CT) 基准集，评估最新密度泛函在 CT 激发方面的性能。为此比较，选择了最先进的范围分离 (RS) 和长程校正 (LC) 双杂化 (DH) 方法，并检查了全局 DH 和 LC 杂化泛函。广泛研究了交换相关 (XC) 能量的正确长程行为，并比较了各种 CT 描述符。结果表明，RS-PBE-P86/SOS-ADC(2) 的性能最稳健，因为它非常适合以出色的准确性描述两种类型的 CT 激发。此外，对于大多数全局 DH，关于分子内跃迁，出乎意料地获得了极好的结果，但也表明了它们对于双分子配合物的局限性。尽管 LC-DH 方法对于常见的分子内激发具有出色的性能，但对于分子间 CT 跃迁，指出了严重的缺陷，并揭示了 XC 能量的错误长程行为。在任何方面都不建议将 LC 杂化应用于此类跃迁。
