Li Musen, Kobayashi Rika, Amos Roger D, Ford Michael J, Reimers Jeffrey R
International Centre for Quantum and Molecular Structures and Department of Physics, Shanghai University Shanghai 200444 China
ANU Supercomputer Facility Leonard Huxley Bldg. 56, Mills Rd Canberra ACT 2601 Australia.
Chem Sci. 2021 Dec 31;13(5):1492-1503. doi: 10.1039/d1sc03738b. eCollection 2022 Feb 2.
Five effects of correction of the asymptotic potential error in density functionals are identified that significantly improve calculated properties of molecular excited states involving charge-transfer character. Newly developed materials-science computational methods are used to demonstrate how these effects manifest in materials spectroscopy. Connection is made considering chlorophyll- as a paradigm for molecular spectroscopy, 22 iconic materials as paradigms for 3D materials spectroscopy, and the V defect in hexagonal boron nitride as an example of the spectroscopy of defects in 2D materials pertaining to nanophotonics. Defects can equally be thought of as being "molecular" and "materials" in nature and hence bridge the relms of molecular and materials spectroscopies. It is concluded that the density functional HSE06, currently considered as the standard for accurate calculations of materials spectroscopy, should be replaced, in most instances, by the computationally similar but asymptotically corrected CAM-B3LYP functional, with some specific functionals for materials-use only providing further improvements.
确定了密度泛函中渐近势误差校正的五种效应，这些效应显著改善了涉及电荷转移特性的分子激发态的计算性质。使用新开发的材料科学计算方法来证明这些效应如何在材料光谱中体现。以叶绿素作为分子光谱的范例、22种标志性材料作为三维材料光谱的范例以及六方氮化硼中的V缺陷作为与纳米光子学相关的二维材料缺陷光谱的示例进行关联。缺陷在本质上同样可以被视为“分子”和“材料”，因此架起了分子光谱和材料光谱的领域之间的桥梁。得出的结论是，目前被视为材料光谱精确计算标准的密度泛函HSE06，在大多数情况下，应被计算上相似但经过渐近校正的CAM - B3LYP泛函所取代，仅一些特定的材料专用泛函能提供进一步的改进。
