Electrostatic Redox Reactions and Charge Storage in Molecular Electronic Junctions
Bibliographic record
Abstract
The electronic properties of a molecular junction (MJ) consisting of a redox-active molecular layer and a 15 nm thick layer of aluminum oxide (AlOx) between conducting carbon contacts were compared to the same device lacking AlOx. For the electron acceptor naphthalene diimide (NDI), a negative bias applied to an NDI/AlOx MJ injects electrons into the NDI, which are blocked from further transport by the oxide. The electrons stored in the NDI more than double the charge storage over that of an equivalent dielectric parallel plate capacitor, and the dynamics of charging and discharging are completely distinct from those of a parallel plate. Replacement of NDI with an electron donor tetraphenylporphyrin (TPP) layer reverses the polarity of the charge/discharge process with electrons leaving the TPP layer under positive bias. The charge/discharge kinetics are temperature and bias dependent, indicating the electrons injected into the NDI layer result in nuclear reorganization to the configuration of an NDI– anion. The devices exhibit electronic properties resembling a “dynamic chemical capacitor”, in which carriers are stored in the molecular layer and the charging kinetics are controlled by reorganization energy, temperature, and applied bias. The molecule/oxide MJs are analogous to an electrochemical cell lacking ions, double layers, and solvent and involve only a single half reaction. In addition to providing kinetic information about basic electron transfer reactions underlying electrochemistry, electron donor–acceptor reactions, and electrostatic effects in organic electronics, the molecule/oxide MJs may have valuable applications in charge storage, memory, and as capacitors with a range of response times tunable by variations in structure and reorganization energy.
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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) | 0.001 | 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".