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Record W1963764661 · doi:10.1139/v05-161

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram

2005· article· en· W1963764661 on OpenAlexvenueno aff
Wei Wu, Sason Shaik, William H. Saunders

Bibliographic record

VenueCanadian Journal of Chemistry · 2005
Typearticle
Languageen
FieldChemistry
TopicInorganic Fluorides and Related Compounds
Canadian institutionsnot available
Fundersnot available
KeywordsChemistryTransition stateValence (chemistry)FluorideIonValence bond theoryAtomic physicsGround stateComputational chemistryCrystallographyPhysical chemistryMolecular orbitalMoleculeInorganic chemistryOrganic chemistryCatalysis

Abstract

fetched live from OpenAlex

A valence bond self-consistent field (VBSCF) calculation has been carried out on the bimolecular elimination (E2) reaction of fluoride ion with ethyl fluoride. The transition state was first optimized at HF/6-31+G and the resulting orbitals were used in the VBSCF calculation. A transition-state hybrid consisting of four structures (F – H-CH 2 -CH 2 -F, F-HCH 2 =CH 2 F – , F-H – CH 2 -CH 2 -F, and F – H-CH 2 -CH 2 + F – ) failed to give a reasonable energy. Incorporation of four charge-separated structures (F – H +– CH 2 -CH 2 -F, F – H +– CH 2 -CH 2 + F – , F – H + CH 2 =CH 2 F – , and F-H – CH 2 -CH 2 + F – ) for a total of eight resulted in an energy slightly below Hartree–Fock. A full-space VBSCF calculation utilizing 50 structures showed that the eight structures give a sufficiently accurate wave function. The transition state is dominated by charge-separated structures, leading to a greater degree of charge separation than in either the reactant or product complex. Therefore, the transition state does not evolve synchronously from the reactants, and explicit allowance should be made for this fact when applying descriptions of the reaction path, such as that in the More O'Ferrall – Jencks diagram. Key words: elimination reaction, E2, transition state, VBSCF calculation, XMVB programs.

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 distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.086
Threshold uncertainty score0.485

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0010.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0000.000

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 head0.015
GPT teacher head0.232
Teacher spread0.218 · 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 teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
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

Citations2
Published2005
Admission routes1
Has abstractyes

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Same venueCanadian Journal of ChemistrySame topicInorganic Fluorides and Related CompoundsFrench-language works237,207