Electric Field Driven Protonation/Deprotonation of Self-Assembled Monolayers of Acid-Terminated Thiols
Bibliographic record
Abstract
Using electrochemical impedance spectroscopy (EIS), we provide an explanation for the pH dependence of the voltammetric peak height for the electric-field-driven protonation and deprotonation of carboxylic acid-terminated thiol self-assembled monolayers (SAMs). The current flowing through the interface can be divided into a purely capacitive current and a protonation/deprotonation current that is directly related to the rate of change of the SAM's protonation (or deprotonation). We demonstrate that at applied potentials close to those corresponding to half-ionization of the SAM and pHs near the pK(1/2), the equivalent circuit describing the interface consists of a Helmholtz film capacity in parallel with a "protonation/deprotonation" impedance which is further shown to be a series combination of a resistor, Rp, and capacitor Cp. Explicit expressions for Rp and Cp are derived in terms of the rate constants for the forward (protonation) and reverse (deprotonation) reactions. Simulated EIS data demonstrate the agreement between our model of the interface and experimental impedance and voltammetric data.
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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".