The Variationally Fitted Electron-Electron Potential

TL;DR

This paper introduces a variational fitting approach for the electron-electron interaction in quantum chemistry, ensuring robust and first-order corrected energies in DFT and Hartree-Fock models, especially for transition metals.

Contribution

It develops a variational method for fitting the electron-electron potential that guarantees energy robustness and first-order error correction in quantum chemical calculations.

Findings

Variational fitting reduces first-order Coulomb errors in transition metal calculations.

The method provides consistent and robust energy differences across different functionals.

First-order exchange and correlation errors are comparable in magnitude.

Abstract

Perhaps the simplest first-principles approach to electronic structure is to fit the charge distribution of each orbital pair and use those fits wherever they appear in the entire electron-electron (EE) interaction energy. The charge distributions in quantum chemistry are typically represented as a sums over products of Gaussian orbital basis functions. If fitted, they are also represented as a sum over single-center Gaussian fitting basis functions. With two representations of the charge distributions, the proper definition of energy is ambiguous. To remedy this, we require that the variation of the energy with respect to a product of orbitals generates a fitted potential. This makes the quantum-mechanical energy robust, i.e. corrected to first order for the error made using an incomplete fitting basis. The coupled orbital and fitting equations are then the result of making the energy stationary with respect to two independent sets of variables. We define the potentials and unique energies for methods based on the Hartree Fock model and variationally fit the full EE interaction in DFT. We compare implementations of variational fitting in DFT at six different levels for three different functionals. Our calculations are performed on transition metal atoms, for which first-order Coulomb errors, due to an incomplete fitting basis sets, are significant. Variational first-order exchange and correlation errors have similar magnitude in all cases. Robust energy differences are much smaller, particularly in the local density approximation.