The one-dimensional nature of polyynes
Bibliographic record
Abstract
Carbyne is a hypothetical carbon allotrope that consists of sp-hybridized carbon atoms in an infinitely-long, one-dimensional (1-D) linear chain. Polyynes, the oligomeric cousins of carbyne, with a dense delocalized-electron framework, could offer groundbreaking electronic properties. We have studied the linear and third-order nonlinear optical properties of both tri<i>iso</i>propylsilyl end-capped (<i>TIPS</i>-PY) and phenyl end-capped (<i>p</i>-PY) polyynes containing pure sp-hybridized carbon backbones. Analysis of the <i>TIPS</i>-polyyne UV-vis absorption spectra shows that the absorption gap, Eg, in these materials scales very precisely as a power-law with increasing oligomer length, n, with Eg~n<sup>-0.379±0.002</sup>. The phenylated polyynes show a similar trend of E<sub>g</sub>~n<sup>-0.36±0.01</sup>. Ultrafast molecular second-hyperpolarizabilities, γ, were obtained in solution using 800nm, 100fs pulses in a differential optical Kerr effect (DOKE) setup. Polyyne second-hyperpolarizabilities also scale with a power-law, and, surprisingly, with exponents higher than that of any other reported oligomer system, yielding a behavior of γ~n<sup>4.3±0.1</sup> and γ~n<sup>3.8±0.1</sup> for the <i>TIPS</i>-polyynes and phenylated-polyynes, respectively. These findings contrast direct theoretical predictions that increases in gamma with increasing conjugation length for polyynes should be considerably lower than those of polyenes and polyenynes. Furthermore, the combined linear and nonlinear optical results agree with recent theoretical studies on ideal 1-D conjugated systems, suggesting that polyynes display true 1-D behavior.
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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 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".