How many distinct and reliable multireference diagnostics are there?

Economical multireference (MR) diagnostics are essential for high-throughput computational studies, enabling the rapid and accurate identification of molecules affected by nondynamic correlation within large molecular datasets. Although various MR diagnostics have been proposed, benchmarking studies that help identify the criteria for an effective diagnostic are still scarce. In this article, we examine a wide range of correlation measures to evaluate their potential as MR diagnostics. We identify a small set of valid size-intensive correlation measures based on maximum metrics, exhibiting similar predictive values. Among these, we highlight INDmax, which offers an easy interpretation: it captures the largest deviation of a natural orbital occupancy from the boundary values corresponding to a single-reference wave function. No energy-based correlation measure was found suitable for constructing MR diagnostics. Finally, we demonstrate how average correlation measures, although not suitable as MR diagnostics, can provide a more comprehensive view of electron correlation within the molecule.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2025-03-24
DOI
https://doi.org/10.1063/5.0250636
Citations
8
Primary Topic
Spectroscopy and Quantum Chemical Studies
Type
article
Field-Weighted Citation Impact
9.97

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article

How many distinct and reliable multireference diagnostics are there?

Eloy Ramos‐Cordoba, Luis Soriano‐Agueda, Xu Xiang, Xabier López et al.
8 citations
The Journal of Chemical Physics
Spectroscopy and Quantum Chemical Studies
9.97
article

How many distinct and reliable multireference diagnostics are there?

Eloy Ramos‐Cordoba, Luis Soriano‐Agueda, Xu Xiang, Xabier López, Eduard Matito
article en
8 citations

Abstract

Economical multireference (MR) diagnostics are essential for high-throughput computational studies, enabling the rapid and accurate identification of molecules affected by nondynamic correlation within large molecular datasets. Although various MR diagnostics have been proposed, benchmarking studies that help identify the criteria for an effective diagnostic are still scarce. In this article, we examine a wide range of correlation measures to evaluate their potential as MR diagnostics. We identify a small set of valid size-intensive correlation measures based on maximum metrics, exhibiting similar predictive values. Among these, we highlight INDmax, which offers an easy interpretation: it captures the largest deviation of a natural orbital occupancy from the boundary values corresponding to a single-reference wave function. No energy-based correlation measure was found suitable for constructing MR diagnostics. Finally, we demonstrate how average correlation measures, although not suitable as MR diagnostics, can provide a more comprehensive view of electron correlation within the molecule.

The Journal of Chemical PhysicsVol. 162(12)
Ikerbasque (ES), University of the Basque Country (ES), Institute of Advanced Chemistry of Catalonia (ES), Donostia International Physics Center (ES), Universidad Nacional Autónoma de México (MX)
Eusko Jaurlaritza, Ministerio de Ciencia e Innovación
Affordable and clean energy
Openalex Percentile: Top 2%
Spectroscopy and Quantum Chemical Studies
9.97
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How many distinct and reliable multireference diagnostics are there? — Eloy Ramos‐Cordoba, Luis Soriano‐Agueda, et al. · The Journal of Chemical Physics (2025) | TGRS Research Map | TGRS