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Record W3186474674 · doi:10.1021/acs.inorgchem.1c00801

Trans Element-Hydrogen Bonds: A Distinctive Difference Between Transition Metals and Main Group Elements

2021· article· en· W3186474674 on OpenAlexafffund
Brian T. H. Tsui, Robert H. Morris

Bibliographic record

VenueInorganic Chemistry · 2021
Typearticle
Languageen
FieldMaterials Science
TopicHydrogen Storage and Materials
Canadian institutionsUniversity of Toronto
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsChemistryHydridePorphyrinGroup (periodic table)CrystallographyAntisymmetric relationTriatomic moleculeMain group elementSinglet stateTransition metalHydrogenHydrogen bondAtomic physicsStereochemistryMoleculePhotochemistryExcited statePhysics

Abstract

fetched live from OpenAlex

The change in sign of the interaction force constant between element-hydrogen stretching modes of trans-dihydrides of the d block and p block elements is analyzed for the first time. As the transition metal M approaches group 12, the higher energy symmetric trans-H–M–H vibration νsym approaches the energy of the antisymmetric vibration νasym. Crossing to group 13 elements E, the trans-H–E–H vibration νsym increasingly drops below νasym. This reversal is attributed to the d orbital that participates in the H–M–H bonding but is nonbonding in the H–E–H compounds. DFT calculations are used to probe the energetics of isoelectronic triatomic [H–M–H]n+ and [H–E–H]n− to reveal this trend and also to demonstrate that the magnitude of these interactions (νgap) increases down groups 11, 12, and 14 but remains fairly constant for group 13. They are also used to show that this reversal is seen in the transition state for hydride transfer to CO2 from the model compounds trans-NiH2(porphyrin) and trans-EH2(porphyrin), E = Si and Ge in their singlet states.

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 categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
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 score0.003
Threshold uncertainty score1.000

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)0.0030.000

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 head0.012
GPT teacher head0.231
Teacher spread0.220 · 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.

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

Citations1
Published2021
Admission routes2
Has abstractyes

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