Piecewise nonlinearity and capacitance in the joint density functional theory of extended interfaces
نویسندگان
چکیده
The ab initio simulation of charged interfaces in the framework density functional theory (DFT) is heavily employed for study electrochemical energy conversion processes. capacitance primary descriptor response interface. It essentially equal to inverse curvature as a function electron number, and such there appears conflict with fundamental principle piecewise linearity DFT that requires be zero at fractional numbers, i.e. almost everywhere. To resolve this conflict, we derive an exact expression between Kohn-Sham states, local Fukui potential. We find requirement does not hold volume- or area-specific extended systems surfaces. Applied joint electrode-electrolyte interface, including ionic dielectric electrolyte, same represents rigorous basis partitioning total interfacial into contributions quantum capacitance, space-charge double-layer capacitance. provides insight influence electrode material, thickness, temperature on charging characteristics, demonstrated by results bulk gold electrode, single-layer graphene electrode.
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ژورنال
عنوان ژورنال: Physical review
سال: 2021
ISSN: ['0556-2813', '1538-4497', '1089-490X']
DOI: https://doi.org/10.1103/physrevb.103.l161403