Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost

Bajaj, Akash; Janet, Jon Paul; Kulik, Heather J.

doi:10.1063/1.5008981

Title: Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost

Journal Article · Tue Nov 21 00:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5008981· OSTI ID:1511169

Bajaj, Akash ^[1]; Janet, Jon Paul ^[1];

^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT) fails to recover the flat plane, exhibiting convex fractional charge errors (FCE) and concave fractional spin errors (FSE) that are related to delocalization and static correlation errors. We previously showed that DFT+U eliminates FCE but now demonstrate that, like other widely employed corrections (i.e., Hartree-Fock exchange), it worsens FSE. To find an alternative strategy, we examine the shape of semi-local DFT deviations from the exact flat plane and we find this shape to be remarkably consistent across ions and molecules. We introduce the judiciously modified DFT (jmDFT) approach, wherein corrections are constructed from few-parameter, low-order functional forms that fit the shape of semi-local DFT errors. Here we select one such physically intuitive form and incorporate it self-consistently to correct semi-local DFT. We demonstrate on model systems that jmDFT represents the first easy-to-implement, no-overhead approach to recovering the flat plane from semi-local DFT.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0018096

OSTI ID:: 1511169

Alternate ID(s):: OSTI ID: 1409703

Journal Information:: Journal of Chemical Physics, Vol. 147, Issue 19; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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