Biradical radiationless decay channel in adenine and its derivatives
Bibliographic record
Abstract
Coupled-cluster calculations of increasing accuracy (approximate doubles: CC2; doubles: EOM-CCSD; connected triples: CR-EOM-CCSD(T)) for CIS-optimized potential energy profiles of adenine and its derivatives indicate that the ultrafast internal conversion of the optically excited π π* state occurs through a state switch to a biradical state, which intersects the ground state at a lower energy. The electronic nature of the biradical state is defined by an electronic configuration in which one unpaired electron occupies a π* orbital confined to the five-membered ring. The second unpaired electron is localized very strongly on a p-type C2 atomic orbital of the six-membered ring. The biradical state minimum has a strongly puckered six-membered ring and a C2–H bond, which is twisted nearly perpendicular to the average ring plane. Consistent with the biradical-mediated internal conversion, the π π* state lifetime is extremely short in adenine and 9-methyladenine, which have barrierless crossing to the biradical state. The lifetime is slightly longer in N,N-dimethyladenine, which has a small barrier for the state switch. In 2-aminopurine the biradical state is found above the π π* state, preventing the biradical state switch and dramatically increasing the lifetime. These results, combined with an earlier work on pyrimidine bases, strongly suggest the importance of a direct decay of the doorway π π* state via a biradical state switch in the photophysics of DNA, even though the nature of the biradical state is somewhat different in purines and pyrimidines.Key words: adenine, guanine, DNA damage, radiationless decay, biradical, ab initio, coupled clusted.
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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".