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Record W4210701012 · doi:10.1021/jasms.1c00354

Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory

2022· article· en· W4210701012 on OpenAlexafffund
Alexander Haack, Justine R. Bissonnette, Christian Ieritano, W. Scott Hopkins

Bibliographic record

VenueJournal of the American Society for Mass Spectrometry · 2022
Typearticle
Languageen
FieldChemistry
TopicAnalytical Chemistry and Chromatography
Canadian institutionsUniversity of Waterloo
FundersDeutsche ForschungsgemeinschaftNatural Sciences and Engineering Research Council of CanadaGovernment of CanadaGovernment of Ontario
KeywordsChemistryIon-mobility spectrometryCluster analysisIonDispersion (optics)Differential (mechanical device)AnalyteChemical physicsStatistical physicsComputational physicsThermodynamicsPhysical chemistryPhysicsStatisticsOrganic chemistry

Abstract

fetched live from OpenAlex

Differential mobility spectrometry is a separation technique that may be applied to a variety of analytes ranging from small molecule drugs to peptides and proteins. Although rudimentary theoretical models of differential mobility exist, these models are often only applied to small molecules and atomic ions without considering the effects of dynamic microsolvation. Here, we advance our theoretical description of differential ion mobility in pure N2 and microsolvating environments by incorporating higher order corrections to two-temperature theory (2TT) and a pseudoequilibrium approach to describe ion-neutral interactions. When comparing theoretical predictions to experimentally measured dispersion plots of over 300 different compounds, we find that higher order corrections to 2TT reduce errors by roughly a factor of 2 when compared to first order. Model predictions are accurate especially for pure N2 environments (mean absolute error of 4 V at SV = 4000 V). For strongly clustering environments, accurate thermochemical corrections for ion–solvent clustering are likely required to reliably predict differential ion mobility behavior. Within our model, general trends associated with clustering strength, solvent vapor concentration, and background gas temperature are well reproduced, and fine structure visible in some dispersion plots is captured. These results provide insight into the dynamic ion–solvent clustering process that underpins the phenomenon of differential ion mobility.

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 imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation 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 score0.245
Threshold uncertainty score0.921

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.002
Bibliometrics0.0000.001
Science and technology studies0.0000.001
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.001
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 head0.016
GPT teacher head0.254
Teacher spread0.238 · 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 teacher head, 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

Citations18
Published2022
Admission routes2
Has abstractyes

Explore more

Same venueJournal of the American Society for Mass SpectrometrySame topicAnalytical Chemistry and ChromatographyFrench-language works237,207