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Record W2079655555 · doi:10.1021/jp001978l

An Electron Localization Function (ELF) Study of the 2-Norbornyl Cation

2000· article· en· W2079655555 on OpenAlexaff
Nick Henry Werstiuk, Heidi M. Muchall, Stéphane Noury

Bibliographic record

VenueThe Journal of Physical Chemistry A · 2000
Typearticle
Languageen
FieldChemistry
TopicFree Radicals and Antioxidants
Canadian institutionsMcMaster University
Fundersnot available
KeywordsElectronElectron localization functionPopulationChemistryWave functionStructural basinValence (chemistry)Physics2-Norbornyl cationAtomic physicsQuantum mechanicsStereochemistryPaleontologyGeology

Abstract

fetched live from OpenAlex

Wave functions obtained at Becke3LYP, Becke3PW91, MP2, and QCISD levels of theory for the 2-norbornyl cation ( 1 ) are used in a topological analysis of the Becke−Edgecombe electron localization function (ELF) with the Silvi suite of programs. Partitioning of the molecular space of the cation into basins of attractors yields information on the shared valence basin interactions at the C1−C2−C6 face of 1 and other C s species in which the C1−C6 and C2−C6 distances are increased incrementally to 193.5 pm. At the Becke3LYP/cc-PVTZ//Becke3LYP/cc-PVTZ level, a single trisynaptic basin with a population of 0.83 electrons connects C1 and C2 to C6 in the optimized geometry where the C1/C2−C6 distances are 188.9 pm. When the C1/C2−C6 distances are increased by 4.5 pm to 193.5 pm, the shared trisynaptic basin splits into a monosynaptic basin at C6 with a population of 0.49 electrons and a disynaptic basin between C1 and C2 with a population of 2.75 electrons; and Δ E T is only 0.12 kcal mol -1 . Disynaptic basins with electron populations in the region of 0.5 electrons link C1−C6 and C2−C6 in the equilibrium optimized geometries of 1 obtained at the MP2, Becke3PW91, and QCISD levels (the C1/C2−C6 distances range from 182.5 to 184.6 pm). This is the case even when the large correlation-consistent basis set cc-PVTZ is used to obtain the wave functions. But these shared interactions are lost when the C1/C2−C6 distances are increased in the range of 8 pm. While the nature of the basins at the C1−C2−C6 face depends on the C1/C2−C6 distances and the basis set, on the whole, increases in energy only ranging up to 0.55 kcal mol -1 are found with large basis sets when the distances are increased by 4−8 pm. At the point where the shared valence interactions between C1/C2 and C6 are lost, there is no discontinuity in the calculated total energy. According to our ELF analysis the formation of 1 from the C s primary “open” cation involves a transfer of electrons from the valence basin of the double bond at C1−C2 to a basin at C6 The stabilization of 1 relative to the open primary cation results from an electrostatic interaction between a carbocation and the electrons of a carbon−carbon double bond.

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 score0.002
Threshold uncertainty score0.403

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 head0.005
GPT teacher head0.231
Teacher spread0.226 · 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

Citations19
Published2000
Admission routes1
Has abstractyes

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