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Title: A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio

Here, a new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio ( m/z), a two-dimensional Ω – m/z space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω – m/z space. Species of the same chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω – m/zmore » space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.« less
Authors:
 [1] ; ORCiD logo [2] ;  [3] ;  [1] ;  [3] ;  [3] ;  [1] ;  [2] ;  [1] ;  [1]
  1. Aerodyne Research Inc., Billerica, MA (United States)
  2. Univ. of Colorado, Boulder, CO (United States); Cooperative Institute for Research in Environmental Sciences, Boulder, CO (United States)
  3. TOFWERK, Thun (Switzerland)
Publication Date:
Grant/Contract Number:
SC0011105
Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 16; Journal Issue: 20; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Research Org:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1360106

Zhang, Xuan, Krechmer, Jordan E., Groessl, Michael, Xu, Wen, Graf, Stephan, Cubison, Michael, Jayne, John T., Jimenez, Jose L., Worsnop, Douglas R., and Canagaratna, Manjula R.. A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio. United States: N. p., Web. doi:10.5194/acp-16-12945-2016.
Zhang, Xuan, Krechmer, Jordan E., Groessl, Michael, Xu, Wen, Graf, Stephan, Cubison, Michael, Jayne, John T., Jimenez, Jose L., Worsnop, Douglas R., & Canagaratna, Manjula R.. A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio. United States. doi:10.5194/acp-16-12945-2016.
Zhang, Xuan, Krechmer, Jordan E., Groessl, Michael, Xu, Wen, Graf, Stephan, Cubison, Michael, Jayne, John T., Jimenez, Jose L., Worsnop, Douglas R., and Canagaratna, Manjula R.. 2016. "A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio". United States. doi:10.5194/acp-16-12945-2016. https://www.osti.gov/servlets/purl/1360106.
@article{osti_1360106,
title = {A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio},
author = {Zhang, Xuan and Krechmer, Jordan E. and Groessl, Michael and Xu, Wen and Graf, Stephan and Cubison, Michael and Jayne, John T. and Jimenez, Jose L. and Worsnop, Douglas R. and Canagaratna, Manjula R.},
abstractNote = {Here, a new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio (m/z), a two-dimensional Ω – m/z space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω – m/z space. Species of the same chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω – m/z space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.},
doi = {10.5194/acp-16-12945-2016},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 20,
volume = 16,
place = {United States},
year = {2016},
month = {10}
}