Non-empirical corrections to DFT

Density functional theory (DFT) is widely applied to both molecules and materials, but well known energetic delocalization and static correlation errors in practical exchange-correlation approximations limit quantitative accuracy. Common methods that correct energetic delocalization error, such as the Hubbard U correction in DFT+U or Hartree-Fock exchange in global hybrids, do so at the cost of worsening static correlation error. We recently introduced an alternate approach known as judiciously modified DFT (jmDFT), wherein the deviation from exact behavior of semi-local functionals over both fractional spin and charge, i.e., the so-called flat plane, was used to motivate functional forms of second order analytic corrections. In this work, we introduce fully non-empirical expressions for all four coefficients in a DFT+U+J-inspired form of jmDFT, where all coefficients are obtained only from energies and eigenvalues of the integer-electron systems. We show good agreement for and coefficients obtained non-empirically as compared against the results of numerical fitting in a jmDFTU+J/J′ correction. Incorporating the fully non-empirical jmDFT correction reduces and even eliminates fractional spin error at the same time as eliminating energetic delocalization error.  We show that this approach extends beyond s-electron systems to higher angular momentum cases including p- and d-electrons. Finally, we diagnose some shortcomings of the current jmDFT approach that limit its ability to improve upon DFT results for cases such as weakly bound anions due to poor underlying semi-local functional behavior.

Check out our recent publication in Journal of Chemical Physics here!

About Us

The Kulik group focuses on the development and application of new electronic structure methods and atomistic simulations tools in the broad area of catalysis.

Our Interests

We are interested in transition metal chemistry, with applications from biological systems (i.e. enzymes) to nonbiological applications in surface science and molecular catalysis.

Our Focus

A key focus of our group is to understand mechanistic features of complex catalysts and to facilitate and develop tools for computationally driven design.

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