Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling
Bibliographic record
Abstract
This paper shows that molecular layers grown using diazonium chemistry on carbon surfaces have properties indicative of the presence of a variety of structural motifs. Molecular layers grown with aromatic monomers with thickness between 1 and ∼15 nm display optical absorption spectra with significant broadening but no change in band gap or onsets of absorption as a function of layer thickness. This suggests that there is no extended conjugation in these layers, contrary to the conclusions of previous work. Density-functional theory modelling of the non-conjugated versions of the constituent aromatic monomers reveals that the experimental trends in optical spectra can be recovered, thereby establishing limits to the degree of conjugation and the nature of the order of as-grown molecular layers. We conclude that the absence of both shifts in band gap and changes in absorption onset is a consequence of resonant conjugation within the layers being less than 1.5 monomer units, and that film disorder is the main origin of the optical spectra. These findings have important implications for understanding charge transport mechanisms in molecular junction devices, as the layers cannot be expected to behave as ideal, resonantly conjugated films, but should be viewed as a collection of mixed nonresonantly- and resonantly-conjugated monomers.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot 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.
Codex and Gemma teacher scores by category
| 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) | 0.000 | 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 teacher head, 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".