An Exchange-Based Diagnostic for Static Correlation

Abstract

We propose here a DFT-based diagnostic for static correlation %TAEX[TPSS@HF - HF] which effectively measures how different the DFT and HF exchange energies for a given HF density are. This and %TAEcorr[TPSS] are two cost-effective a priori estimates for the adequacy of the importance of static correlation. %TAEX[TPSS@HF - HF] contains nearly the same information as the earlier A diagnostic, but may be more intuitive to understand. Principal component and variable clustering analysis of a large number of static correlation diagnostics reveals much of the variation is explained by just two components, and almost all of it by four; these are blocked by four variable clusters (single excitations; correlation entropy; double excitations; pragmatic energetics).

5 pages, AIP Conference Proceedings, in press (ICCMSE-2021)

References in corpus (5)

• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• W3 theory: robust computational thermochemistry in the kJ/mol accuracy range
• Basis set convergence of post-CCSD contributions to molecular atomization energies
• The Importance of being consistent
• Separation of Dynamic and Nondynamic Correlation

Cited by in corpus (1)

• The MOBH35 metal-organic barrier heights reconsidered: performance of local-orbital coupled cluster approaches in different static correlation regimes