The photolysis of α-hydroperoxycarbonyls

Physical Chemistry Chemical Physics : PCCP
Zhen LiuJ Peeters

Abstract

In this work, we theoretically elucidated the mechanism and predicted the major products of the photolysis of α-hydroperoxycarbonyls, known to be products of the atmospheric oxidation of biogenic volatile organic compounds (BVOC) and components of secondary organic aerosol (SOA) in rural and remote areas. Using 2-hydroperoxypropanal OCHCH(OOH)CH3as a model compound, we show that the likely major photolysis mechanism is a fast 1,5 H-shift in the initially excited singlet S1state followed by spontaneous elimination of singlet oxygen to yield an enol HOCH[double bond, length as m-dash]CHCH3, while intersystem crossing (ISC) to the triplet T1state and C-C scission into HC˙O + HOOC˙HCH3followed by expulsion of a hydroxyl radical from the unstable HOOC˙HCH3is another product channel. The direct S1reaction was found to occur at such a high rate that the quantum yield in atmospheric conditions is expected to approach unity. In the atmosphere, the enol should generally react with OH radicals or tautomerize into the more stable carbonyl O[double bond, length as m-dash]CH-CH2CH3. Vinylalcohol is shown to be a major end product of the photolysis of hydroperoxyacetaldehyde, an isoprene oxidation product. Taking into account also the importa...Continue Reading

References

Jun 25, 2005·The Journal of Chemical Physics·Jamie MatthewsJoseph S Francisco
Jul 10, 2009·Physical Chemistry Chemical Physics : PCCP·J PeetersL Vereecken
Oct 1, 2010·Physical Chemistry Chemical Physics : PCCP·Jozef Peeters, Jean-François Müller
Jun 28, 2011·Physical Chemistry Chemical Physics : PCCP·John D CrounsePaul O Wennberg
Apr 21, 2012·Physical Chemistry Chemical Physics : PCCP·Glenn M WolfeFrank N Keutsch
Nov 7, 2012·Environmental Science & Technology·R Suarez-BertoaJ-F Doussin
Feb 28, 2014·Nature·Mikael EhnThomas F Mentel
May 23, 2014·Environmental Science & Technology·Sui SoGabriel da Silva
Dec 9, 2014·The Journal of Physical Chemistry. a·Eric PraskePaul O Wennberg
May 28, 2015·Proceedings of the National Academy of Sciences of the United States of America·Tuija JokinenMikko Sipilä
Sep 4, 2015·The Journal of Physical Chemistry. a·Jason M St ClairPaul O Wennberg
Sep 4, 2015·The Journal of Physical Chemistry. a·Rebecca H SchwantesPaul O Wennberg
Jan 2, 2016·The Journal of Physical Chemistry Letters·Jozef PeetersJean-François Müller
Dec 16, 2016·The Journal of Physical Chemistry. a·Torsten BerndtMarkku Kulmala
Apr 12, 2017·Journal of the American Chemical Society·Alexander P TengPaul O Wennberg

❮ Previous
Next ❯

Citations

May 8, 2021·Environmental Science & Technology·Veronika PospisilovaJay G Slowik
Dec 15, 2018·The Journal of Physical Chemistry. a·Eric PraskePaul O Wennberg

❮ Previous
Next ❯

Methods Mentioned

BETA
irradiating

Software Mentioned

Tinker
Molpro
Gaussian
ORCA

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.