Wodyński Artur, Kaupp Martin
Technische Universität Berlin, Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Straße des 17. Juni 135, D-10623 Berlin, Germany.
J Chem Theory Comput. 2025 Aug 12;21(15):7419-7429. doi: 10.1021/acs.jctc.5c00699. Epub 2025 Jul 18.
Recent work has shown that range-separated local hybrid (RSLH) functionals containing correction terms for strong correlation and delocalization errors, such as ωLH23tdE, allow a remarkable paradigm change in the context of the usual zero-sum game between delocalization and static correlation errors in the development of density functional approximations. In this work, we evaluate the modification of the dynamical correlation contribution for such strong correlation-corrected RSLHs (scRSLHs) and how it affects the performance of the large GMTKN55 database of main-group thermochemistry, kinetics, and noncovalent interactions. Replacing the B95c correlation in the previous functionals by a more flexible reoptimized B97c power-series expansion leads to substantial improvements. The ωLH25tdE scRSLH provides a GMTKN55 WTMAD-2 value of 2.64 kcal/mol in self-consistent calculations, when augmented by DFT-D4 corrections. This is the lowest for any rung 4 functional today. At the same time, ωLH25tdE retains the favorable performance for spin-restricted bond dissociation, the removal of unphysical spin contamination in certain open-shell transition-metal complexes, and the correct long-range asymptotic potential, resulting in excellent results for quasiparticle computations of ionization potentials, electron affinities, and band gaps.
最近的研究表明，包含强关联和离域误差校正项的范围分离局部杂化（RSLH）泛函，如ωLH23tdE，在密度泛函近似发展中离域和静态关联误差之间通常的零和博弈背景下，带来了显著的范式转变。在这项工作中，我们评估了这种强关联校正的RSLH（scRSLH）的动态关联贡献的修正及其对主族热化学、动力学和非共价相互作用的大型GMTKN55数据库性能的影响。用更灵活的重新优化的B97c幂级数展开取代先前泛函中的B95c关联，带来了实质性的改进。当通过DFT-D4校正增强时，ωLH25tdE scRSLH在自洽计算中提供了2.64 kcal/mol的GMTKN55 WTMAD-2值。这是目前任何第4级泛函中的最低值。同时，ωLH25tdE在自旋限制键解离、去除某些开壳过渡金属配合物中不物理的自旋污染以及正确的长程渐近势方面保持了良好的性能，从而在电离势、电子亲和能和带隙的准粒子计算中得到了出色的结果。
