Interfaces select specific stereochemical conformations: The isomerization of glyoxal at the liquid water interface

Chongqin Zhu, Sabre Kais, Xiao Cheng Zeng, Joseph S. Francisco, Ivan Gladich

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Interfacial chemistry involving glyoxal at aerosol surfaces is postulated to catalyze aerosol growth. This chemistry remains speculative due to a lack of detailed information concerning the physicochemical behavior of glyoxal at the interface of atmospheric aerosols. Here, we report results from high-level electronic structure calculations as well as both classical and Born-Oppenheimer ab initio molecular dynamics simulations °f glyoxal solvation at the air/liquid water interface. When compared to the gas phase, the trans to cis isomerization of glyoxal at the liquid water interface is found to be catalyzed; additionally, the trans conformation is selectively solvated within the bulk to a greater degree than is the cis conformation. These two processes, i.e., the catalytic effect at the water interface and the differentially selective solvation, act to enhance the concentration of the cis isomer of glyoxal at the water interface. This has important consequences for the interpretation of experiments and for the modeling of glyoxal chemistry both at the interface of water clouds and at aerosols. Broader implications of this work relate to describing the role of interfaces in selecting specific stereo molecular structures at interfacial environments.

Original languageEnglish
Pages (from-to)27-30
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number1
DOIs
Publication statusPublished - 11 Jan 2017

Fingerprint

Glyoxal
Isomerization
Conformations
Aerosols
Water
Liquids
Solvation
Atmospheric aerosols
Surface chemistry
Isomers
Molecular structure
Electronic structure
Molecular Dynamics Simulation
Molecular dynamics
Molecular Structure
Gases
Air
Computer simulation
Growth
Experiments

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Interfaces select specific stereochemical conformations : The isomerization of glyoxal at the liquid water interface. / Zhu, Chongqin; Kais, Sabre; Zeng, Xiao Cheng; Francisco, Joseph S.; Gladich, Ivan.

In: Journal of the American Chemical Society, Vol. 139, No. 1, 11.01.2017, p. 27-30.

Research output: Contribution to journalArticle

Zhu, Chongqin ; Kais, Sabre ; Zeng, Xiao Cheng ; Francisco, Joseph S. ; Gladich, Ivan. / Interfaces select specific stereochemical conformations : The isomerization of glyoxal at the liquid water interface. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 1. pp. 27-30.
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