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Record W2164713858 · doi:10.1021/jp011472i

A Quantum Chemical and TST Study of the OH Hydrogen-Abstraction Reaction from Substituted Aldehydes:  FCHO and ClCHO

2001· article· en· W2164713858 on OpenAlexafffund
Nelaine Mora‐Diez, J. Raúl Alvarez‐Idaboy, Russell J. Boyd

Bibliographic record

VenueThe Journal of Physical Chemistry A · 2001
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsDalhousie University
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsHydrogen atom abstractionTransition state theoryChemistryAb initioReaction rate constantComputational chemistryHydrogenBasis setReaction mechanismPhysical chemistryQuantum tunnellingChemical kineticsTransition stateKineticsDensity functional theoryCatalysisPhysicsOrganic chemistryQuantum mechanics

Abstract

fetched live from OpenAlex

In the present study, ab initio methods have been used to study the OH hydrogen-abstraction reaction from two substituted aldehydes: FCHO and ClCHO. A complex mechanism in which the overall rate depends on the rates of two competitive reactions, a reversible step where a reactant (or prereactive) complex is formed, followed by the irreversible hydrogen abstraction to form the products, is corroborated. This mechanism was previously shown to describe accurately the kinetics of the OH hydrogen-abstraction reaction from formaldehyde and acetaldehyde. Classical transition state theory (TST) rate constants calculated with tunneling corrections, assuming an unsymmetrical Eckart barrier, agree very well with experimental upper bound values. Activation energy barriers and enthalpies of reaction have been estimated through CCSD(T) single point calculations using MP2 geometries and frequencies and the 6-311++G(d,p) basis set.

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 score0.031
Threshold uncertainty score0.420

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 studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
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 head0.011
GPT teacher head0.252
Teacher spread0.241 · 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

Citations50
Published2001
Admission routes2
Has abstractyes

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