Journal ArticleDOI
Atmospheric fate of methacrolein. 1. Peroxy radical isomerization following addition of OH and O2.
John D. Crounse,Hasse C. Knap,Kristian Baruël Ørnsø,Solvejg Jørgensen,Fabien Paulot,Henrik G. Kjaergaard,Paul O. Wennberg +6 more
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TLDR
Simulations using a global chemical transport model suggest that most of the methacrolein hydroxy peroxy radicals formed in the atmosphere undergo isomerization and decomposition.Abstract:
Peroxy radicals formed by addition of OH and O2 to the olefinic carbon atoms in methacrolein react with NO to form methacrolein hydroxy nitrate and hydroxyacetone. We observe that the ratio of these two compounds, however, unexpectedly decreases as the lifetime of the peroxy radical increases. We propose that this results from an isomerization involving the 1,4-H-shift of the aldehydic hydrogen atom to the peroxy group. The inferred rate (0.5 ± 0.3 s–1 at T = 296 K) is consistent with estimates obtained from the potential energy surface determined by high level quantum calculations. The product, a hydroxy hydroperoxy carbonyl radical, decomposes rapidly, producing hydroxyacetone and re-forming OH. Simulations using a global chemical transport model suggest that most of the methacrolein hydroxy peroxy radicals formed in the atmosphere undergo isomerization and decomposition.read more
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A large source of low-volatility secondary organic aerosol
Mikael Ehn,Joel A. Thornton,Einhard Kleist,Mikko Sipilä,Heikki Junninen,Iida Pullinen,Monika Springer,Florian Rubach,Ralf Tillmann,Ben H. Lee,Felipe D. Lopez-Hilfiker,S. Andres,Ismail-Hakki Acir,Matti P. Rissanen,Tuija Jokinen,Siegfried Schobesberger,Juha Kangasluoma,Jenni Kontkanen,Tuomo Nieminen,Theo Kurtén,Lasse B. Nielsen,Solvejg Jørgensen,Henrik G. Kjaergaard,Manjula R. Canagaratna,Miikka Dal Maso,Torsten Berndt,Tuukka Petäjä,Andreas Wahner,Veli-Matti Kerminen,Markku Kulmala,Douglas R. Worsnop,Juergen Wildt,Thomas F. Mentel +32 more
TL;DR: It is found that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies.
Journal ArticleDOI
Recent advances in understanding secondary organic aerosol: Implications for global climate forcing
Manish Shrivastava,Christopher D. Cappa,Jiwen Fan,Allen H. Goldstein,Alex Guenther,Jose L. Jimenez,Chongai Kuang,Alexander Laskin,Scot T. Martin,Nga L. Ng,Tuukka Petäjä,Jeffrey R. Pierce,Philip J. Rasch,Pontus Roldin,John H. Seinfeld,John E. Shilling,James N. Smith,Joel A. Thornton,Rainer Volkamer,Jian Wang,Douglas R. Worsnop,Rahul A. Zaveri,Alla Zelenyuk,Qi Zhang +23 more
TL;DR: In this paper, a review summarizes some of the important developments during the past decade in understanding secondary organic aerosol (SOA) formation, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity.
Journal ArticleDOI
Autoxidation of Organic Compounds in the Atmosphere
TL;DR: In this paper, it was shown that the rate of abstraction of hydrogen by peroxy radicals is largely determined by the thermochemistry of the nascent alkyl radicals and thus is highly influenced by neighboring substituents.
Journal ArticleDOI
Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol
F. Bianchi,Theo Kurtén,Matthieu Riva,Claudia Mohr,Matti P. Rissanen,Pontus Roldin,Torsten Berndt,John D. Crounse,Paul O. Wennberg,Thomas F. Mentel,Jürgen Wildt,Heikki Junninen,Heikki Junninen,Tuija Jokinen,Markku Kulmala,Douglas R. Worsnop,Joel A. Thornton,Neil M. Donahue,Henrik G. Kjaergaard,Mikael Ehn +19 more
TL;DR: This Review defines HOM and describes the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties.
Journal ArticleDOI
Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance
TL;DR: In this review, laboratory studies of this peroxy radical chemistry are detailed, as they pertain to the chemistry of the atmosphere, particularly pertaining to the complex chemistry associated with the atmospheric oxidation of biogenic hydrocarbons.
References
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Journal ArticleDOI
Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
Journal ArticleDOI
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
Journal ArticleDOI
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.
Journal ArticleDOI
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
TL;DR: In this article, two extended basis sets (termed 5-31G and 6 -31G) consisting of atomic orbitals expressed as fixed linear combinations of Gaussian functions are presented for the first row atoms carbon to fluorine.
Journal ArticleDOI
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
TL;DR: In this paper, a modified basis set of supplementary diffuse s and p functions, multiple polarization functions (double and triple sets of d functions), and higher angular momentum polarization functions were defined for use with the 6.31G and 6.311G basis sets.
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