MétaCan
Menu
Back to cohort
Record W2599858903 · doi:10.1039/c7cp00691h

Revisiting the definition of local hardness and hardness kernel

2017· article· en· W2599858903 on OpenAlex

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.
fundA Canadian funder is recorded on the work.

Bibliographic record

VenuePhysical Chemistry Chemical Physics · 2017
Typearticle
Languageen
FieldEngineering
TopicEnergetic Materials and Combustion
Canadian institutionsMcMaster University
FundersConsejo Nacional de Ciencia y Tecnología, GuatemalaNatural Sciences and Engineering Research Council of CanadaConsejo Nacional de Ciencia y Tecnología
KeywordsKernel (algebra)ElectrophileMathematicsSpace (punctuation)ElectronMathematical analysisPure mathematicsChemistryPhysicsQuantum mechanicsOrganic chemistryComputer science

Abstract

fetched live from OpenAlex

An analysis of the hardness kernel and local hardness is performed to propose new definitions for these quantities that follow a similar pattern to the one that characterizes the quantities associated with softness, that is, we have derived new definitions for which the integral of the hardness kernel over the whole space of one of the variables leads to local hardness, and the integral of local hardness over the whole space leads to global hardness. A basic aspect of the present approach is that global hardness keeps its identity as the second derivative of energy with respect to the number of electrons. Local hardness thus obtained depends on the first and second derivatives of energy and electron density with respect to the number of electrons. When these derivatives are approximated by a smooth quadratic interpolation of energy, the expression for local hardness reduces to the one intuitively proposed by Meneses, Tiznado, Contreras and Fuentealba. However, when one combines the first directional derivatives with smooth second derivatives one finds additional terms that allow one to differentiate local hardness for electrophilic attack from the one for nucleophilic attack. Numerical results related to electrophilic attacks on substituted pyridines, substituted benzenes and substituted ethenes are presented to show the overall performance of the new definition.

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.

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 score0.017
Threshold uncertainty score0.495

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 head0.015
GPT teacher head0.219
Teacher spread0.204 · 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