Localization in the SCAN meta-generalized gradient approximation functional leading to broken symmetry ground states for graphene and benzene

Zhang, Yubo1,2,3,4; Zhang, Wenqing1,2,3,4; Singh, David J.5,6

2020-09-21

10.1039/d0cp03567j

PHYSICAL CHEMISTRY CHEMICAL PHYSICS   影响因子和分区

1463-9076

1463-9084

Density functional theory calculations play a central role in understanding chemical and solid-state systems. Progress depends on density functionals that accurately reproduce both energies, for thermochemistry, and properly describe ground states and other properties that are of interest. The Cr dimer, benzene and graphene are particularly important benchmark systems for quantum chemistry and condensed matter physics. The Strongly Constrained and Appropriately Normed (SCAN) functional, which is an advanced meta-generalized gradient approximation functional that significantly improves molecular energies is shown to perform poorly for the Cr dimer. This is connected with its poor performance for itinerant solid-state magnets and is a consequence of over localization of electrons, thus illustrating an analogy between the Cr dimer and itinerant magnets. The Cr dimer is a notoriously difficult system for density functionals. However, we additionally find that SCAN predicts an incorrect symmetry broken ground state for 2D graphene and for the benzene molecule, which is surprising considering that ground states of these are known to be well described even by the simplest local density approximation. We show that SCAN overly favors localized spin polarized states, which is a serious deficiency of this approach. Thus, the challenge of finding density functionals that accurately treat both localized and delocalized electronic systems remains.

SCI ; EI

英语

第一 ; 通讯

U.S. Department of Energy, Office of Science, Basic Energy Sciences[DE-SC0019114] ; National Natural Science Foundation of China[11904156] ; Guangdong Innovation Research Team Project[2017ZT07C062] ; Guangdong Provincial Key-Lab Program[2019B030301001] ; Shenzhen Municipal Key-Lab program[ZDSYS20190902092905285]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:000571344300012

ROYAL SOC CHEMISTRY

20204309392976

Quantum chemistry ; Graphene ; Ground state ; Benzene ; Magnets

Nanotechnology:761 ; Physical Chemistry:801.4 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Organic Polymers:815.1.1

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Phys, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Inst Quantum Sci Sc Engn, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Computat Sci & Mat Design, Shenzhen 518055, Guangdong, Peoples R China
4.Southern Univ Sci & Technol, Shenzhen Municipal Key Lab Adv Quantum Mat & Devi, Shenzhen 518055, Guangdong, Peoples R China
5.Univ Missouri, Dept Phys & Astron, Columbia, MO 65211 USA
6.Univ Missouri, Dept Chem, Columbia, MO 65211 USA

Zhang, Yubo,Zhang, Wenqing,Singh, David J.. Localization in the SCAN meta-generalized gradient approximation functional leading to broken symmetry ground states for graphene and benzene[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2020,22(35):19585-19591.

Zhang, Yubo,Zhang, Wenqing,&Singh, David J..(2020).Localization in the SCAN meta-generalized gradient approximation functional leading to broken symmetry ground states for graphene and benzene.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,22(35),19585-19591.

Zhang, Yubo,et al."Localization in the SCAN meta-generalized gradient approximation functional leading to broken symmetry ground states for graphene and benzene".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 22.35(2020):19585-19591.