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Record W1906110380 · doi:10.1039/b303698g

Hyperfine coupling constants, electron-spin g-factors and vertical spectra of the X<sup>2</sup>Σ<sup>+</sup>radicals BeH, MgH, CaH and BZ<sup>+</sup>, AlZ<sup>+</sup>, GaZ<sup>+</sup>(Z = H, Li, Na, K). A theoretical study

2003· article· en· W1906110380 on OpenAlexaff
Pablo J. Bruna, Friedrich Grein

Bibliographic record

VenuePhysical Chemistry Chemical Physics · 2003
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsUniversity of New Brunswick
Fundersnot available
KeywordsHyperfine structureChemistryAtomic physicsValence (chemistry)Wave functionUnpaired electronSpectral lineIntramolecular forceConfiguration interactionAb initioRadicalCoupling constantValence electronElectron transferElectronHyperfine couplingAnalytical Chemistry (journal)Excited statePhysicsPhysical chemistryStereochemistry

Abstract

fetched live from OpenAlex

Hyperfine coupling constants (hfcc), electron-spin g-factors, excitation energies (ΔE) and oscillator strengths (f-values) are calculated for the X2Σ+ (1σ22σ) radicals YH (Y = Be, Mg, Ca) and BZ+, AlZ+, GaZ+ (Z = H, Li, Na, K). Single reference ab initio and density functional theory methods are used for the hfcc's, and multireference configuration interaction wavefunctions for ΔE's, f-values and g-shifts. In XZ+ (X = B to Ga; Z = Li to K), the 2σ unpaired electron is 60–90% pσ(X), resulting in |A⊥| being one order of magnitude larger than |A‖|. The Δg⊥'s are relatively large for just 3 valence electrons, from −3300 to −6100 ppm for BZ+, −14 100 to −29 600 ppm for AlZ+, and −93 700 to −198 300 ppm for GaZ+. Such large Δg⊥(XZ+)'s relate to the strong coupling between the close-lying X2Σ+ and 12Π(2σ → 1π) states, which results from the splitting of the 2P(s2p) state of X due to its interaction with Z+. ESR spectra are not available for any of the XZ+'s. Calculation on the hydrides YH/XH+ reproduce well the experimental hfcc's and g factors, except for AlH+, which appears to be strongly perturbed in Ar matrices. Several transitions X2Σ+ → n2Σ+ and X2Σ+ → n2Π in XZ+ have large oscillator strengths, mainly caused by intramolecular charge-transfer processes X ↔ Z and atomic-like sg ↔ pu excitations.

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)0.001
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Science and technology studies, Research integrity
Consensus categoriesMeta-epidemiology (narrow)
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 score0.113
Threshold uncertainty score0.998

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.001
Meta-epidemiology (narrow)0.0030.003
Meta-epidemiology (broad)0.0040.002
Bibliometrics0.0000.002
Science and technology studies0.0010.006
Scholarly communication0.0000.001
Open science0.0020.002
Research integrity0.0010.005
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 head0.008
GPT teacher head0.242
Teacher spread0.234 · 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; both teacher heads agree on what is shown here.

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

Citations36
Published2003
Admission routes1
Has abstractyes

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