School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.
J Chem Theory Comput. 2011 Mar 8;7(3):602-9. doi: 10.1021/ct1005517. Epub 2011 Jan 18.
We have evaluated the performance of several density functional theory (DFT) functionals for the description of the ground-state electronic structure and charge transfer in donor/acceptor complexes. The tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) complex has been considered as a model test case. Hybrid functionals have been chosen together with recently proposed long-range corrected functionals (ωB97X, ωB97X-D, LRC-ωPBEh, and LC-ωPBE) in order to assess the sensitivity of the results to the treatment and magnitude of exact exchange. The results show an approximately linear dependence of the ground-state charge transfer with the HOMOTTF-LUMOTCNQ energy gap, which in turn depends linearly on the percentage of exact exchange in the functional. The reliability of ground-state charge transfer values calculated in the framework of a monodeterminantal DFT approach was also examined.
我们评估了几种密度泛函理论（DFT）函数对于描述给体/受体复合物的基态电子结构和电荷转移的性能。四硫富瓦烯-四氰基对醌二甲烷（TTF-TCNQ）复合物被选为模型测试案例。我们选择了混合泛函以及最近提出的长程修正泛函（ωB97X、ωB97X-D、LRC-ωPBEh 和 LC-ωPBE），以评估结果对精确交换处理和程度的敏感性。结果表明，基态电荷转移与 HOMOTTF-LUMOTCNQ 能隙之间存在近似线性关系，而后者又与函数中精确交换的百分比呈线性关系。我们还检查了在单行列式 DFT 方法框架下计算基态电荷转移值的可靠性。
