Doubly hybrid density functionals that correctly describe both density and energy for atoms

作者：Su, Neil Qiang; Zhu, Zhenyu; Xu, Xin^*

来源：Proceedings of the National Academy of Sciences, 2018, 115(10): 2287-2292.

DOI：10.1073/pnas.1713047115

• density functional theory
• electron density
• electronic structure
• doubly hybrid functional
• XYG3

Recently, it was argued [Medvedev MG, et al. (2017) Science 355: 49-52] that the development of density functional approximations (DFAs) is "straying from the path toward the exact functional." The exact functional should yield both exact energy and density for a system of interest; nevertheless, they found that many heavily fitted functionals for molecular energies actually lead to poor electron densities of atoms. They also observed a trend that, for the nonempirical and few-parameter functionals, densities can be improved as one climbs up the first four rungs of the Jacob's ladder of DFAs. The XYG3 type of doubly hybrid functionals (xDHs) represents a less-empirical and fewer-parameter functional on the top fifth rung, in which both the Hartree-Focklike exchange and the second-order perturbative (MP2-like) correlation are hybridized with the low rung functionals. Here, we show that xDHs can well describe both density and energy for the same atomic set of Medvedev et al., showing that the latter trend can well be extended to the top fifth rung.

• 出版日期2018-3-6
• 单位复旦大学