Gauging aromatic conjugation and charge delocalization in the aryl silanes Ph<sub>n</sub>SiH<sub>4−n</sub> (<i>n</i> = 0–4), with silicon K-edge XAS and TDDFT
Bibliographic record
Abstract
Si K-edge X-ray absorption spectra (XAS) have been measured experimentally and calculated using time-dependent density functional theory (TDDFT) to investigate electronic structure in aryl silanes, PhnSiH4-n (n = 0-4). Adding aryl groups to SiH4 splits the Si-H σ-antibonding orbitals into new orbitals with Si-Ph π-bonding (πb) and π-antibonding (π*) character. Greater aryl substitution is reflected by increasingly intense Si 1s → πb and Si 1s → π* transitions, and weaker transitions into the Si-H and Si-C σ* orbitals. These observations are consistent with known trends in the hydride donor ability of aryl silanes, which is driven in part by the composition of the LUMOs and the accessibility of pathways for electron delocalization through aromatic conjugation. Methodology developed for liquid-phase Si K-edge XAS measurements on PhSiH3 and Ph2SiH2 will enable dynamic studies of chemical transformations involving silicon-containing catalysts, intermediates, and substrates.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 0.000 |
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.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
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".