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 int...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.展开更多
基金supported by the National Natural Science Foundation of China(No.21973015,No.22125301,No.91427301)the Science Challenge Project(TZ2018004)+1 种基金Innovative Research Team of High-Level Local universities in Shanghaia Key Laboratory Program of the Education Commission of Shanghai Municipality(ZDSYS14005)。
文摘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.
