Toward chemical accuracy at low computational cost: Density-functional theory with σ-functionals for the correlation energy

We introduce new functionals for the Kohn-Sham correlation energy that are based on the adiabatic-connection fluctuation-dissipation (ACFD) theorem and are named sigma -functionals. Like in the well-established direct random phase approximation (dRPA), sigma -functionals require as input exclusively eigenvalues sigma of the frequency-dependent KS response function. In the new functionals, functions of sigma replace the sigma -dependent dRPA expression in the coupling-constant and frequency integrations contained in the ACFD theorem. We optimize sigma -functionals with the help of reference sets for atomization, reaction, transition state, and non-covalent interaction energies. The optimized functionals are to be used in a post-self-consistent way using orbitals and eigenvalues from conventional Kohn-Sham calculations employing the exchange-correlation functional of Perdew, Burke, and Ernzerhof. The accuracy of the presented approach is much higher than that of dRPA methods and is comparable to that of high-level wave function methods. Reaction and transition state energies from sigma -functionals exhibit accuracies close to 1 kcal/mol and thus approach chemical accuracy. For the 10 966 reactions of the W4-11RE reference set, the mean absolute deviation is 1.25 kcal/mol compared to 3.21 kcal/mol in the dRPA case. Non-covalent binding energies are accurate to a few tenths of a kcal/mol. The presented approach is highly efficient, and the post-self-consistent calculation of the total energy requires less computational time than a density-functional calculation with a hybrid functional and thus can be easily carried out routinely. sigma -Functionals can be implemented in any existing dRPA code with negligible programming effort.

Automated summary

The introduced sigma-Functionals are based on the ACFD theorem and optimized for reaction and transition state energies, achieving accuracies close to 1 kcal/mol and approaching chemical accuracy. With mean absolute deviation of 1.25 kcal/mol for 10,966 reactions, the approach is more accurate than dRPA methods and comparable to high-level wave function methods. Non-covalent binding energies are also accurately predicted to within a few tenths of a kcal/mol. The method is highly efficient, requiring less computational time than a density-functional calculation with a hybrid functional and can be easily implemented in existing dRPA codes.