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Issue 37, 2016
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Density functional theory and an experimentally-designed energy functional of electron density

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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.

Graphical abstract: Density functional theory and an experimentally-designed energy functional of electron density

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Publication details

The article was received on 10 Mar 2016, accepted on 22 Aug 2016 and first published on 26 Aug 2016


Article type: Paper
DOI: 10.1039/C6CP01659F
Citation: Phys. Chem. Chem. Phys., 2016,18, 25984-25992
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    Density functional theory and an experimentally-designed energy functional of electron density

    D. A. Miranda and P. R. Bueno, Phys. Chem. Chem. Phys., 2016, 18, 25984
    DOI: 10.1039/C6CP01659F

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