XC100: A Wavefunction-Derived Exchange-Correlation Energy Dataset for Atomic and Molecular Species

Abstract

A workflow is introduced for constructing accurate, wavefunction-derived Kohn-Sham (KS) exchange-correlation (XC) energies across atomic and molecular species. Correlated total energies and densities are obtained from configuration interaction wave functions in a polarized triple-zeta basis, cc-pVTZ, and each wavefunction density is then mapped onto a KS determinant. A composite correction adds valence and core basis functions (cc-pVQZ and cc-pCVTZ), plus a two-point Riemann extrapolation to approach the complete-basis-set limit. The workflow is applied to 100 closed-shell atomic and molecular species composed of main group elements to form the XC100 data set. The resulting KS densities closely reproduce the correlated densities, with a median L2/Ne difference of 1.42 X 10^{-5}, while the composite corrections recover substantial correlation energy beyond the cc-pVTZ reference. Comparison with conventional and machine-learned density functional approximations gives insight into the quality of Exc across different types of models for XC. In all, this paper's workflow demonstrates a practical route for generating XC reference data for the assessment and development of density functionals.