Does a Molecule-Specific
Density Functional Give an
Accurate Electron Density? The Challenging Case of the
CuCl Electric Field Gradient
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Abstract
In the framework of determining system-specific long-range
corrected
density functionals, the question is addressed whether such functionals,
tuned to satisfy the condition −ε<sup>HOMO</sup> = IP
or other energetic criteria, provide accurate electron densities.
A nonempirical physically motivated two-dimensional tuning of range-separated
hybrid functionals is proposed and applied to the particularly challenging
case of a molecular property that depends directly on the ground-state
density: the copper electric field gradient (EFG) in CuCl. From a
continuous range of functional parametrizations that closely satisfy −ε<sup>HOMO</sup> = IP and the correct asymptotic behavior of the potential,
the one that best fulfills the straight-line behavior of <i>E</i>(<i>N</i>), the energy as a function of a fractional electron
number <i>N</i>, was found to provide the most accurate
electron density as evidenced by calculated EFGs. The functional also performs
well for related Cu systems