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Localizing Electron Density Errors in Density Functional Theory

submitted on 06.05.2019 and posted on 07.05.2019 by Rubén Laplaza, Victor Polo, Julia Contreras-García
This work attempts to provide a clear picture on the relative quality of different Density Functional Approximations through the use of Quantum Chemical Topology on molecular electronic densities. In particular, two simple yet ever-important systems are studied, the N2 and CO molecules. Our results exemplify how real-space descriptors can clearly assess the calculated electronic density of a molecular system, avoiding unwanted error compensation present in simplified statistical metrics. Errors in ``well'' built functionals are shown to be concentrated in chemically meaningful regions of space, and hence they are predictable. Conversely, strongly parametrized functionals show isotropic errors that cannot be traced back to chemical transferable units. Moreover, we will show that energetic corrections are mapped back into improvements in the density in chemically meaningful regions. These results point at the relevance of real-space perspectives when parametrizing or assessing energy and density errors.


Email Address of Submitting Author


Sorbonne Université / Universidad de Zaragoza


France / Spain

ORCID For Submitting Author


Declaration of Conflict of Interest

We declare no conflict of interest.

Version Notes

Version 1.