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arxiv: 1602.03267 · v1 · pith:C6JXEZ2Tnew · submitted 2016-02-10 · ⚛️ physics.chem-ph

Ground-State Energy as a Simple Sum of Orbital Energies in Kohn-Sham Theory: A Shift in Perspective through a Shift in Potential

classification ⚛️ physics.chem-ph
keywords leftrightmathbfenergyground-statepotentialwhenapproximation
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It is observed that the exact interacting ground-state electronic energy of interest may be obtained directly, in principle, as a simple sum of orbital energies when a universal density-dependent term is added to $w\left(\left[ \rho \right];\mathbf{r} \right)$, the familiar Hartree plus exchange-correlation component in the Kohn-Sham effective potential. The resultant shifted potential, $\bar{w}\left(\left[ \rho \right];\mathbf{r} \right)$, actually changes less on average than $w\left(\left[ \rho \right];\mathbf{r} \right)$ when the density changes, including the fact that $\bar{w}\left(\left[ \rho \right];\mathbf{r} \right)$ does not undergo a discontinuity when the number of electrons increases through an integer. Thus the approximation of $\bar{w}\left(\left[ \rho \right];\mathbf{r} \right)$ represents an alternative direct approach for the approximation of the ground-state energy and density.

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