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Record W4283774473 · doi:10.1002/wcms.1631

Delocalization error: The greatest outstanding challenge in density‐functional theory

2022· article· en· W4283774473 on OpenAlexafffund
Kyle R. Bryenton, Adebayo A. Adeleke, Stephen G. Dale, Erin R. Johnson

Bibliographic record

VenueWiley Interdisciplinary Reviews Computational Molecular Science · 2022
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsDalhousie University
FundersNatural Sciences and Engineering Research Council of CanadaAustralian Research CouncilKillam Trusts
KeywordsDensity functional theoryDelocalized electronComputer scienceInterpretation (philosophy)Orbital-free density functional theoryStatistical physicsElectron delocalizationClass (philosophy)Theoretical computer scienceArtificial intelligenceTime-dependent density functional theoryComputational chemistryQuantum mechanicsPhysicsChemistry

Abstract

fetched live from OpenAlex

Abstract Every day, density‐functional theory (DFT) is routinely applied to computational modeling of molecules and materials with the expectation of high accuracy. However, in certain situations, popular density‐functional approximations (DFAs) have the potential to give substantial quantitative, and even qualitative, errors. The most common class of error is delocalization error, which is an overarching term that also encompasses the one‐electron self‐interaction error. In our opinion, its resolution remains the greatest outstanding challenge in DFT development. In this paper, we review the history of delocalization error and provide several complimentary conceptual pictures for its interpretation, along with illustrative examples of its various manifestations. Approaches to reduce delocalization error are discussed, as is its interplay with other shortcomings of popular DFAs, including treatment of non‐bonded repulsion and neglect of London dispersion. This article is categorized under: Electronic Structure Theory > Density Functional Theory

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.008
metaresearch head score (Gemma)0.017
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Theoretical or conceptual · Consensus signal: Theoretical or conceptual
GenreCandidate signal: Empirical · Consensus signal: none
Teacher disagreement score0.008
Threshold uncertainty score0.043

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0080.017
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0010.001
Science and technology studies0.0010.005
Scholarly communication0.0020.005
Open science0.0020.002
Research integrity0.0020.005
Insufficient payload (model declined to judge)0.0020.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.026
GPT teacher head0.309
Teacher spread0.283 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designTheoretical or conceptual
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations190
Published2022
Admission routes2
Has abstractyes

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