title: Density functional theory and an experimentally-designed energy functional of electron density.
abstract: We herein demonstrate that capacitance spectroscopy (CS) experimentally allows access to the energy associated with the quantum mechanical ground state of many-electron systems. Priorly, electrochemical capacitance, C[small mu, Greek, macron][ρ], was previously understood from conceptual and computational density functional theory (DFT) calculations. Thus, we herein propose a quantum mechanical experiment-based variational method for electron charging processes based on an experimentally-designed functional of the ground state electron density. In this methodology, the electron state density, ρ, and an energy functional of the electron density, E[small mu, Greek, macron][ρ], can be obtained from CS data. CS allows the derivative of the electrochemical potential with respect to the electron density, (δ[small mu, Greek, macron][ρ]/δρ), to be obtained as a unique functional of the energetically minimised system, i.e., β/C[small mu, Greek, macron][ρ], where β is a constant (associated with the size of the system) and C[small mu, Greek, macron][ρ] is an experimentally observable quantity. Thus the ground state energy (at a given fixed external potential) can be obtained simply as E[small mu, Greek, macron][ρ], from the experimental measurement of C[small mu, Greek, macron][ρ]. An experimental data-set was interpreted to demonstrate the potential of this quantum mechanical experiment-based variational principle.
authors.affiliation: Universidad Industrial de Santander, Cra 27 Cll 9, Bucaramanga, Colombia. dalemir@uis.edu.co.
authors.forename: David A
authors.initials: DA
authors.lastname: Miranda
authors.affiliation: Univ. Estadual Paulista (UNESP), Nanobionics group, CP 355, Araraquara, São Paulo 14800-060, Brazil. prbueno@iq.unesp.br.
authors.forename: Paulo R
authors.identifier: http://orcid.org/0000-0003-2827-0208
authors.initials: PR
authors.lastname: Bueno