Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface

Ross D. Hoehn, Marcelo A. Carignano, Sabre Kais, Chongjing Zhu, Jie Zhong, Xiao C. Zeng, Joseph S. Francisco, Ivan Gladich

Research output: Contribution to journalArticle

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Abstract

Methylamine is an abundant amine compound detected in the atmosphere which can affect the nature of atmospheric aerosol surfaces, changing their chemical and optical properties. Molecular dynamics simulation results show that methylamine accommodation on water is close to unity with the hydrophilic head group solvated in the interfacial environment and the methyl group pointing into the air phase. A detailed analysis of the hydrogen bond network indicates stronger hydrogen bonds between water and the primary amine group at the interface, suggesting that atmospheric trace gases will likely react with the methyl group instead of the solvated amine site. These findings suggest new chemical pathways for methylamine acting on atmospheric aerosols in which the methyl group is the site of orientation specific chemistry involving its conversion into a carbonyl site providing hydrophilic groups for uptake of additional water. This conversion may explain the tendency of aged organic aerosols to form cloud condensation nuclei. At the same time, formation of NH 2 radical and formaldehyde is suggested to be a new source for NH 2 radicals at aerosol surfaces, other than by reaction of absorbed NH 3 . The results have general implications for the chemistry of other amphiphilic organics, amines in particular, at the surface of atmospherically relevant aerosols.

Original languageEnglish (US)
Article number214701
JournalJournal of Chemical Physics
Volume144
Issue number21
DOIs
StatePublished - Jun 7 2016

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accommodation
Amines
Hydrogen bonds
Aerosols
aerosols
Atmospheric aerosols
Water
air
amines
hydrogen
Air
water
chemistry
Chemical properties
Formaldehyde
hydrogen bonds
Molecular dynamics
condensation nuclei
Condensation
Optical properties

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface. / Hoehn, Ross D.; Carignano, Marcelo A.; Kais, Sabre; Zhu, Chongjing; Zhong, Jie; Zeng, Xiao C.; Francisco, Joseph S.; Gladich, Ivan.

In: Journal of Chemical Physics, Vol. 144, No. 21, 214701, 07.06.2016.

Research output: Contribution to journalArticle

Hoehn, RD, Carignano, MA, Kais, S, Zhu, C, Zhong, J, Zeng, XC, Francisco, JS & Gladich, I 2016, 'Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface', Journal of Chemical Physics, vol. 144, no. 21, 214701. https://doi.org/10.1063/1.4950951
Hoehn, Ross D. ; Carignano, Marcelo A. ; Kais, Sabre ; Zhu, Chongjing ; Zhong, Jie ; Zeng, Xiao C. ; Francisco, Joseph S. ; Gladich, Ivan. / Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface. In: Journal of Chemical Physics. 2016 ; Vol. 144, No. 21.
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