Computational Studies of the Interaction between Ruthenium Dyes and X<sup>−</sup> and X<sub>2</sub><sup>−</sup>, X = Br, I, At. Implications for Dye-Sensitized Solar Cells
Bibliographic record
Abstract
Quantum chemistry in the form of relativistic density functional theory (DFT) combined with a continuum solvation model has been applied to study the interaction of two prototypical ruthenium dyes (N3 and its chlorinated form) and redox mediators X − and X 2 −, X = Br, I, At, with a view at the elementary reactions within a dye-sensitized solar cell (DSSC). Along the series Br, I, and At, increasing bond lengths of X 2, X 2 −, and X 3 − are found, as well as an increasing reducing power of the X − /X 3 − redox couple. Inner-sphere seven-coordinate complexes between the dye and the redox species do not exist; however, the dyes form outer-sphere complexes with the X − and X 2 − species. The thermodynamics of a recently proposed mechanism [ J. Phys. Chem. C 2007, 111, 6561] involving a [dye + X − ] intermediate are probed, and the existence of the intermediate and the elementary steps of the process are confirmed. The dye regeneration is thermodynamically more favorable for the N3 dye than its chlorinated counterpart. The regeneration of the neutral dye is favored for At, followed by the iodine and bromine systems (At > I > Br). This may be related to the observed superior performance in actual DSSCs of the iodide/triiodide redox couple over the alternative bromide/tribromide couple.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 |
| 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".