Assessment of Advanced xDH@B3LYP Methods in Describing Various Potential Energy Curves Driven byπ-π,CH/π,and SH/πNon-Bonded Interactions  

系统测评xDHB3LYP密度泛函方法在描述π-π、CH/π、和SH/π等非键相互作用中的表现

作　　者：Shiqian Tan Yizhen Wang Igor Ying Zhang Xin Xu 谭诗乾;王艺臻;张颖;徐昕(复旦大学化学系,上海市分子催化与创新材料重点实验室,上海市生物活性小分子重点实验室,计算物理科学教育部重点实验室,能源材料化学协同创新中心,上海200433)

机构地区：[1]Collaborative Innovation Center of Chemistry for Energy Materials,Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,MOE Key Laboratory of Computational Physical Sciences,Shanghai Key Laboratory of Bioactive·Small Molecules,Department of Chemistry,Fudan University,Shanghai 200433,China

出　　处：《Chinese Journal of Chemical Physics》2022年第5期720-726,I0011,共8页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.21973015,No.22125301,No.91427301);the Science Challenge Project(TZ2018004);Innovative Research Team of High-Level Local universities in Shanghai;a Key Laboratory Program of the Education Commission of Shanghai Municipality(ZDSYS14005)。

摘　　要：Accurate description of potential energy curves driven by nonbonded interactions remains a great challenge for pure density functional approximations(DFAs).It is because the Rdecay behavior of dispersion cannot be intrinsically captured by the(semi)-local ingredients and the exact-exchange used in the popular hybrid DFAs.Overemphasizing the accuracy on the equilibrium region for the functional construction would likely deteriorate the overall performance on the other regions of potential energy surfaces.In consequence,the empirical dispersion correction becomes the standard component in DFAs to treat the non-bonded interactions.In this Letter,we demonstrate that without the use of empirical dispersion correction,doubly hybrid approximations,in particular two recently proposed rev XYG3 and XYG7 functionals,hold the promise to have a balanced description of non-bonded interactions on the whole potential energy curves for several prototypes ofπ-π,CH/π,and SH/πinteractions.The error of rev XYG3 and XYG7 for non-bonded interactions is around 0.1 kcal/mol,and their potential energy curves almost coincide with the accurate CCSD(T)/CBS curves.

关 键 词：Density functional theory Non-bonded interaction Doubly hybrid approximations xDH@B3LYP model 

分 类 号：O641.1[理学—物理化学]