Comprehensive benchmarking of density matrix functional approximations

Abstract

The energy usually serves as a yardstick in assessing the performance of approximate methods in computational chemistry. After all, these methods are mostly used for the calculation of the electronic energy of chemical systems. However, computational methods should be also aimed at reproducing other properties, such strategy leading to more robust approximations with a wider range of applicability. In this study, we suggest a battery of ten tests with the aim to analyze density matrix functional approximations (DMFAs), including several properties that the exact functional should satisfy. The tests are performed on a model system with varying electron correlation, carrying a very small computational effort. Our results not only put forward a complete and exhaustive benchmark test for DMFAs, currently lacking, but also reveal serious deficiencies of existing approximations that lead to important clues in the construction of more robust DMFAs.