Theoretical and Computational Chemistry

A Framework for Quantifying Uncertainty in DFT Energy Corrections

Abstract

In this work, we demonstrate a method to quantify uncertainty in corrections to density functional theory (DFT) energies based on empirical results. Such corrections are commonly used to improve the accuracy of computational enthalpies of formation, phase stability predictions, and other energy-derived properties, for example. We incorporate this method into a new DFT energy correction scheme comprising a mixture of oxidation-state and composition-dependent corrections and show that many chemical systems contain unstable polymorphs that may actually be predicted stable when uncertainty is taken into account. We then illustrate how these uncertainties can be used to estimate the probability that a compound is stable on a compositional phase diagram, thus enabling better-informed assessments of compound stability.

Content

Thumbnail image of MP2020_Corrections_Manuscript.pdf
download asset MP2020_Corrections_Manuscript.pdf 1 MB [opens in a new tab]

Supplementary material

Thumbnail image of calc_compounds.json.tgz
download asset calc_compounds.json.tgz 0.02 MB [opens in a new tab]
calc compounds.json
Thumbnail image of correction_calculator_demo_v4.json
download asset correction_calculator_demo_v4.json 3 MB [opens in a new tab]
correction calculator demo v4
Thumbnail image of exp_compounds.json.tgz
download asset exp_compounds.json.tgz 0.03 MB [opens in a new tab]
exp compounds.json
Thumbnail image of expt_formation_enthalpy_kingsbury.json
download asset expt_formation_enthalpy_kingsbury.json 0.43 MB [opens in a new tab]
expt formation enthalpy kingsbury

Supplementary weblinks