TY - JOUR
T1 - Understanding band gaps of solids in generalized Kohn–Sham theory
JF - Proceedings of the National Academy of Sciences
JO - Proc Natl Acad Sci USA
SP - 2801
LP - 2806
M3 - 10.1073/pnas.1621352114
VL - 114
IS - 11
AU - Perdew, John P.
AU - Yang, Weitao
AU - Burke, Kieron
AU - Yang, Zenghui
AU - Gross, Eberhard K. U.
AU - Scheffler, Matthias
AU - Scuseria, Gustavo E.
AU - Henderson, Thomas M.
AU - Zhang, Igor Ying
AU - Ruzsinszky, Adrienn
AU - Peng, Haowei
AU - Sun, Jianwei
AU - Trushin, Egor
AU - Görling, Andreas
Y1 - 2017/03/14
UR - http://www.pnas.org/content/114/11/2801.abstract
N2 - Semiconductors and insulators have a fundamental energy gap and absorb light at a continuum of photon energies above this gap. They also have a band structure of one-electron energies, and a band gap separating unoccupied from occupied one-electron states. When should these gaps be equal? It is known that they are not equal in the exact Kohn–Sham density-functional theory but are equal in commonly used density-functional approximations, such as the generalized gradient approximation (GGA). We show here that they are also equal (and improved) in higher level approximations, such as the meta-GGA or the hybrid of GGA with exact exchange, when the effective one-electron potential is not constrained to be a multiplication operator.The fundamental energy gap of a periodic solid distinguishes insulators from metals and characterizes low-energy single-electron excitations. However, the gap in the band structure of the exact multiplicative Kohn–Sham (KS) potential substantially underestimates the fundamental gap, a major limitation of KS density-functional theory. Here, we give a simple proof of a theorem: In generalized KS theory (GKS), the band gap of an extended system equals the fundamental gap for the approximate functional if the GKS potential operator is continuous and the density change is delocalized when an electron or hole is added. Our theorem explains how GKS band gaps from metageneralized gradient approximations (meta-GGAs) and hybrid functionals can be more realistic than those from GGAs or even from the exact KS potential. The theorem also follows from earlier work. The band edges in the GKS one-electron spectrum are also related to measurable energies. A linear chain of hydrogen molecules, solid aluminum arsenide, and solid argon provide numerical illustrations.
ER -