Semilocal density functional theory with correct surface asymptotics

Abstract

Semilocal density functional theory is the most used computational method for electronic structure calculations in theoretical solid-state physics and quantum chemistry of large systems, providing good accuracy with a very attractive computational cost. Nevertheless, because of the non-locality of the exchange-correlation hole outside a metal surface, it was always considered inappropriate to describe the correct surface asymptotics. Here, we derive, within the semilocal density functional theory formalism, an exact condition for the image-like surface asymptotics of both the exchange-correlation energy per particle and potential. We show that this condition can be easily incorporated into a practical computational tool, at the simple meta-generalized-gradient approximation level of theory. Using this tool, we also show that the Airy-gas model exhibits asymptotic properties that are closely related to the ones at metal surfaces. This result highlights the relevance of the linear effective potential model to the metal surface asymptotics.

6 pages, 4 figures

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Cited by in corpus (9)

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• Assessing exchange-correlation functional performance for structure and property predictions of oxyfluoride compounds from first principles
• No-go theorem for the description of Mott phenomena with conventional Density Functional Theory methods
• Improving the applicability of the Pauli kinetic energy density based semilocal functional for solids
• Hartree potential dependent exchange functional
• Density functional descriptions of interfacial electronic structure
• Investigation of the exchange-correlation potential of functionals based on the adiabatic connection interpolation
• Highly excited electronic image states of metallic nanorings