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

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Autoren

  • Alexander Haack
  • Justine R. Bissonnette
  • Christian Ieritano
  • W. Scott Hopkins

Externe Organisationen

  • University of Waterloo
Forschungs-netzwerk anzeigen

Details

OriginalspracheEnglisch
Seiten (von - bis)535-547
Seitenumfang13
FachzeitschriftJournal of the American Society for Mass Spectrometry
Jahrgang33
Ausgabenummer3
Frühes Online-Datum31 Jan. 2022
PublikationsstatusVeröffentlicht - 2 März 2022
Extern publiziertJa

Abstract

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.

ASJC Scopus Sachgebiete

Zitieren

Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory. / Haack, Alexander; Bissonnette, Justine R.; Ieritano, Christian et al.
in: Journal of the American Society for Mass Spectrometry, Jahrgang 33, Nr. 3, 02.03.2022, S. 535-547.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Haack A, Bissonnette JR, Ieritano C, Hopkins WS. Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory. Journal of the American Society for Mass Spectrometry. 2022 Mär 2;33(3):535-547. Epub 2022 Jan 31. doi: 10.1021/jasms.1c00354
Haack, Alexander ; Bissonnette, Justine R. ; Ieritano, Christian et al. / Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory. in: Journal of the American Society for Mass Spectrometry. 2022 ; Jahrgang 33, Nr. 3. S. 535-547.
Download
@article{9f34ad2d9bdd493999bdb24e6ef32cc5,
title = "Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory",
abstract = "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.",
keywords = "collision cross section, density functional theory, differential ion mobility, ion−solvent cluster, two-temperature theory",
author = "Alexander Haack and Bissonnette, {Justine R.} and Christian Ieritano and Hopkins, {W. Scott}",
note = "Funding Information: We acknowledge the high-performance computing support from Compute Canada. W.S.H. acknowledges financial support provided by the Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of Discovery and Alliance grants as well as the government of Ontario for an Ontario Early Researcher Award. A.H. gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - 449651261. J.R.B. acknowledges financial support from the NSERC Undergraduate Student Research Award (USRA). C.I. acknowledges financial support from the Government of Canada through the Vanier Canada Graduate Scholarship. ",
year = "2022",
month = mar,
day = "2",
doi = "10.1021/jasms.1c00354",
language = "English",
volume = "33",
pages = "535--547",
journal = "Journal of the American Society for Mass Spectrometry",
issn = "1044-0305",
publisher = "Springer New York",
number = "3",

}

Download

TY - JOUR

T1 - Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory

AU - Haack, Alexander

AU - Bissonnette, Justine R.

AU - Ieritano, Christian

AU - Hopkins, W. Scott

N1 - Funding Information: We acknowledge the high-performance computing support from Compute Canada. W.S.H. acknowledges financial support provided by the Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of Discovery and Alliance grants as well as the government of Ontario for an Ontario Early Researcher Award. A.H. gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - 449651261. J.R.B. acknowledges financial support from the NSERC Undergraduate Student Research Award (USRA). C.I. acknowledges financial support from the Government of Canada through the Vanier Canada Graduate Scholarship.

PY - 2022/3/2

Y1 - 2022/3/2

N2 - 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.

AB - 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.

KW - collision cross section

KW - density functional theory

KW - differential ion mobility

KW - ion−solvent cluster

KW - two-temperature theory

UR - http://www.scopus.com/inward/record.url?scp=85124032087&partnerID=8YFLogxK

U2 - 10.1021/jasms.1c00354

DO - 10.1021/jasms.1c00354

M3 - Article

C2 - 35099948

AN - SCOPUS:85124032087

VL - 33

SP - 535

EP - 547

JO - Journal of the American Society for Mass Spectrometry

JF - Journal of the American Society for Mass Spectrometry

SN - 1044-0305

IS - 3

ER -