All-Purpose Measure of Electron Correlation for Multireference Diagnostics

Abstract

We present an analytical relationship between two natural orbital occupancy-based indices, Formula Presented and INDmax, and two established electron correlation metrics: the leading term of a configuration interaction expansion, c0, and the D2 diagnostic. Numerical validation revealed that Formula Presented and INDmax can effectively substitute for c0 and D2, respectively. These indices offer three distinct advantages: (i) they are universally applicable across all electronic structure methods, (ii) their interpretation is more intuitive, and (iii) they can be readily incorporated into the development of hybrid electronic structure methods. Additionally, we draw a distinction between correlation measures and correlation diagnostics, establishing MP2 and CCSD numerical thresholds for INDmax, which are to be used as a multireference diagnostic. Our findings further demonstrate that establishing thresholds for other electronic structure methods can be easily accomplished using small data sets.