Journal article
Absorption spectra and aqueous photochemistry of β-hydroxyalkyl nitrates of atmospheric interest
Molecular physics, Vol.113(15-16), pp.2179-2190
08/18/2015
DOI: 10.1080/00268976.2015.1017020
Abstract
Molar absorption coefficients were measured for select alkyl nitrates and β-hydroxyalkyl nitrates in methanol. The presence of the β-hydroxyl group has a relatively minor effect on the absorption spectrum in the vicinity of the weak n → π* transition, which is responsible for photolysis of organic nitrates in the atmosphere. For both alkyl nitrates and β-hydroxyalkyl nitrates, there is an enhancement in the absorption coefficients in solution compared to the gas-phase values. The effect of the β-hydroxyl group on the spectra was modelled with molecular dynamics simulations using an OM2/GUGA-CI Hamiltonian for ethyl nitrate and β-hydroxyethyl nitrate. The simulation provided a qualitatively correct shape of the low energy tail of the absorption spectrum, which is important for atmospheric photochemistry. The role of direct aqueous photolysis in removal of β-hydroxyalkyl nitrates in cloud and fog water was modelled using a relative rate approach, and shown to be insignificant relative to gas-phase photochemical processes and aqueous OH oxidation under typical atmospheric conditions.
Details
- Title: Subtitle
- Absorption spectra and aqueous photochemistry of β-hydroxyalkyl nitrates of atmospheric interest
- Creators
- Dian E Romonosky - Department of Chemistry, University of CaliforniaLucas Q Nguyen - Department of Chemistry, University of CaliforniaDorit Shemesh - Fritz Haber Center for Molecular Dynamics, The Hebrew UniversityTran B Nguyen - Department of Chemistry, University of CaliforniaScott A Epstein - Department of Chemistry, University of CaliforniaDavid B.C Martin - Department of Chemistry, University of CaliforniaChristopher D Vanderwal - Department of Chemistry, University of CaliforniaR. Benny Gerber - Fritz Haber Center for Molecular Dynamics, The Hebrew UniversitySergey A Nizkorodov - Department of Chemistry, University of California
- Resource Type
- Journal article
- Publication Details
- Molecular physics, Vol.113(15-16), pp.2179-2190
- DOI
- 10.1080/00268976.2015.1017020
- ISSN
- 0026-8976
- eISSN
- 1362-3028
- Publisher
- Taylor & Francis
- Language
- English
- Date published
- 08/18/2015
- Academic Unit
- Iowa Neuroscience Institute; Chemistry
- Record Identifier
- 9984065856702771
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