All-Purpose Measure of Electron Correlation for Multireference Diagnostics.

We present an analytical relationship between two natural orbital occupancy-based indices, I N D ¯ and I ND max , and two established electron correlation metrics: the leading term of a configuration interaction expansion, c 0 , and the D 2 diagnostic. Numerical validation revealed that I N D ¯ and I ND max can effectively substitute for c 0 and D 2 , 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 I ND max , 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.