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Record W4312214615 · doi:10.1021/acs.jpcc.2c06412

Influence of the Hydrogen-Bonding Environment on Vibrational Coupling in the Electrical Double Layer at the Silica/Aqueous Interface

2022· article· en· W4312214615 on OpenAlexafffund
Shyam Parshotam, Benjamin Rehl, Franziska Busse, Alex Brown, Julianne M. Gibbs

Bibliographic record

VenueThe Journal of Physical Chemistry C · 2022
Typearticle
Languageen
FieldPhysics and Astronomy
TopicSpectroscopy and Quantum Chemical Studies
Canadian institutionsUniversity of Alberta
FundersNatural Sciences and Engineering Research Council of CanadaQueen Elizabeth ScholarsTechnische Universität MünchenDeutsche ForschungsgemeinschaftUniversity of Alberta
KeywordsIntermolecular forceIntramolecular forceHydrogen bondRotational–vibrational couplingChemistryChemical physicsMolecular vibrationInfrared spectroscopyElectrokinetic phenomenaAqueous solutionSpectral lineCoupling (piping)Molecular physicsMoleculeAnalytical Chemistry (journal)Materials sciencePhysical chemistryStereochemistryOrganic chemistry

Abstract

fetched live from OpenAlex

Vibrational spectroscopy is a powerful tool for determining the local hydrogen-bonding environment. However, vibrational coupling present in H 2 O makes it difficult to relate vibrational spectra to a molecular description of the system. While numerous bulk studies have shed light on this phenomenon, the influence of both intra- and intermolecular vibrational coupling on the resulting electrical double layer spectra at buried interfaces remains largely unexplored. By utilizing vibrational sum frequency generation (vSFG), electrokinetic measurements, and the maximum entropy method on isotopically diluted water (HOD) at the silica/aqueous interface, we reveal the influence of vibrational coupling on the Stern and diffuse layer spectra as the pH is varied. For the Stern layer spectra, we observe differences in the frequency centers at pH 2 that are less significant at higher pH, signifying the presence of intermolecular coupling that can be related to the double-donor hydrogen-bonded structure of water. Furthermore, the differences in the evolution of the Stern layer of H 2 O and HOD suggest that the presence of intramolecular coupling in the former may distort the spectral response. Moreover, we observe that the evolution of HOD closely matches the p K a of the out-of-plane silanols predicted by previous molecular dynamic simulations.

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 machine prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.001
Threshold uncertainty score0.003

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0010.000

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.

Opus teacher head0.010
GPT teacher head0.250
Teacher spread0.240 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations16
Published2022
Admission routes2
Has abstractyes

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Same venueThe Journal of Physical Chemistry CSame topicSpectroscopy and Quantum Chemical StudiesFrench-language works237,207