Theory Department
Max Planck Institute of Microstructure Physics
1997    
1998    
1999    
2000    
2001    
2002    
2003    
2004    
2005    
2006    
2007    
2008    
2009    
2010    
2011    
2012    
2013    
2014    
2015    
2016    
2017    
2018    
2019    
2020    
2021    
Perdew, J. P., Yang, W., Burke, K., Yang, Z., Gross, E. K. U., Scheffler, M., Scuseria, G. E., Henderson, Th. M., Zhang, I. Y., Ruzsinsky, A., Peng, H., Sun, J., Trushin, E., Görling, A.

Understanding band gaps of solids in generalized Kohn-Sham theory
Proceedings of the National Academy of Sciences 114, (11),pp 2801-2806 (2017)
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.

TH-2017-10