From the Kohn-Sham band gap to the fundamental gap in solids. An integer electron approach

• Published in: Physical chemistry chemical physics : PCCP 2017-06, Vol.19 (24), p.15639-15656
• Main Author: Baerends, E. J
• Format: Article
• Language: English
• Subjects: Approximation; Derivatives; Discontinuity; Energy gaps (solid state); Excitation; Ground state; Integers; Mathematical analysis
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c7cp02123b

It is often stated that the Kohn-Sham occupied-unoccupied gap in both molecules and solids is "wrong". We argue that this is not a correct statement. The KS theory does not allow to interpret the exact KS HOMO-LUMO gap as the fundamental gap (difference ( I − A ) of electron affinity ( A ) and ionization energy ( I ), twice the chemical hardness), from which it indeed differs, strongly in molecules and moderately in solids. The exact Kohn-Sham HOMO-LUMO gap in molecules is much below the fundamental gap and very close to the much smaller optical gap (first excitation energy), and LDA/GGA yield very similar gaps. In solids the situation is different: the excitation energy to delocalized excited states and the fundamental gap ( I − A ) are very similar, not so disparate as in molecules. Again the Kohn-Sham and LDA/GGA band gaps do not represent ( I − A ) but are significantly smaller. However, the special properties of an extended system like a solid make it very easy to calculate the fundamental gap from the ground state (neutral system) band structure calculations entirely within a density functional framework. The correction Δ from the KS gap to the fundamental gap originates from the response part v resp of the exchange-correlation potential and can be calculated very simply using an approximation to v resp . This affords a calculation of the fundamental gap at the same level of accuracy as other properties of crystals at little extra cost beyond the ground state bandstructure calculation. The method is based on integer electron systems, fractional electron systems (an ensemble of N - and ( N + 1)-electron systems) and the derivative discontinuity are not invoked. The upshift Δ of the level at the bottom of the conduction band (the LUMO) from the neutral N -electron crystal to the negative N + 1 system, and therefore the fundamental gap LUMO ( N + 1) − HOMO ( N ) = I − A , can be calculated simply and cheaply from the response part of v xc .