Transformation of Organics in the Unpolluted Atmosphere

The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone

J Sun, S So, G da Silva

2017-10-15

We report a novel mechanism for the interconversion of 2-hydroxypropanal with its more-stable ketone isomer hydroxyacetone. Reacti..

Bonding of aqueous citrate with Zn2 and ZnO nanoclusters: A theoretical study

CCR Sutton, G Da Silva, GV Franks

2017-02-23

To gain insight into how citrate bonds to ZnO, we have studied how aqueous citrate bonds to zinc cations (Zn²⁺) as well..

Gas-Phase Mechanisms of the Reactions of Reduced Organic Nitrogen Compounds with OH Radicals

N Borduas, JPD Abbatt, JG Murphy, S So, G Da Silva

2016-11-01

Research on the fate of reduced organic nitrogen compounds in the atmosphere has gained momentum since the identification of their..

Gas Phase Oxidation of Nicotine by OH Radicals: Kinetics, Mechanisms, and Formation of HNCO

N Borduas, JG Murphy, C Wang, G Da Silva, JPD Abbatt

2016-09-13

Cigarette smoke is recognized as having harmful health effects for the smoker and for people breathing second-hand smoke. In an at..

Decomposition of Pyruvic Acid on the Ground-State Potential Energy Surface

G Da Silva

2016-01-21

A potential energy surface is reported for isomerization and decomposition of gas-phase pyruvic acid (CH<inf>3</inf>C(O)C(O)OH) in..

A Theoretical Study of the Photoisomerization of Glycolaldehyde and Subsequent OH Radical-Initiated Oxidation of 1,2-Ethenediol

S So, U Wille, G Da Silva

2015-09-24

It has recently been discovered that carbonyl compounds can undergo UV-induced isomerization to their enol counterparts under atmo..

Experimental and theoretical understanding of the gas phase oxidation of atmospheric amides with OH radicals: Kinetics, products, and mechanisms

N Borduas, G Da Silva, JG Murphy, JPD Abbatt

2015-05-14

Atmospheric amides have primary and secondary sources and are present in ambient air at low pptv levels. To better assess the fate..

Modeling the IR spectra of aqueous metal carboxylate complexes: Correlation between bonding geometry and stretching mode wavenumber shifts

CCR Sutton, G Da Silva, GV Franks

2015-04-27

A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be u..

Modeling the antisymmetric and symmetric stretching vibrational modes of aqueous carboxylate anions

CCR Sutton, GV Franks, G Da Silva

2015-01-05

The infrared spectra of six aqueous carboxylate anions have been calculated at the M05-2X/cc-pVTZ level of theory with the SMD sol..

Are the three hydroxyphenyl radical isomers created equal?-The role of the phenoxy radical -

P Hemberger, G Da Silva, AJ Trevitt, T Gerber, A Bodi

2015-01-01

We have investigated the thermal decomposition of the three hydroxyphenyl radicals (C<inf>6</inf>H<inf>4</inf>OH) in a heated micr..

Unimolecular reaction chemistry of a charge-tagged beta-hydroxyperoxyl radical

S So, BB Kirk, AJ Trevitt, U Wille, SJ Blanksby, G da Silva

2014-10-22

β-Hydroxyperoxyl radicals are formed during atmospheric oxidation of unsaturated volatile organic compounds such as isoprene. They..

Direct versus water-mediated protodecarboxylation of acetic acid catalyzed by group 10 carboxylates, [(phen)M(O2CCH3)]

M Woolley, GN Khairallah, G Da Silva, PS Donnelly, RAJ Ohair

2014-10-13

The gas-phase protodecarboxylation of acetic acid catalyzed by group 10 metal complexes was examined using a combination of multis..

Atmospheric chemistry of enols: A theoretical study of the vinyl alcohol OH O2 reaction mechanism

S So, U Wille, G Da Silva

2014-06-17

Enols are emerging as trace atmospheric components that may play a significant role in the formation of organic acids in the atmos..

Reaction of benzene with atomic carbon: Pathways to fulvenallene and the fulvenallenyl radical in extraterrestrial atmospheres and the interstellar medium

G Da Silva

2014-06-05

The reaction of benzene with ground-state atomic carbon, C(³P), has been investigated using the G3X-K composite quantum..

Isomer-specific product detection of gas-phase xylyl radical rearrangement and decomposition using VUV synchrotron photoionization

P Hemberger, AJ Trevitt, T Gerber, E Ross, G Da Silva

2014-05-22

Xylyl radicals are intermediates in combustion processes since their parent molecules, xylenes, are present as fuel additives. In ..

Hydroxyl radical formation in the gas phase oxidation of distonic 2-methylphenyl radical cations

MB Prendergast, PA Cooper, BB Kirk, G Da Silva, SJ Blanksby, AJ Trevitt

2013-12-21

The reactions of distonic 4-(N,N,N-trimethylammonium)-2-methylphenyl and 5-(N,N,N-trimethylammonium)-2-methylphenyl radical cation..

Photoisomerization action spectroscopy of the carbocyanine dye DTC in the gas phase

BD Adamson, NJA Coughlan, G Da Silva, EJ Bieske

2013-12-19

Molecular photoisomerization plays a crucial role in diverse biological and technological contexts. Here, we combine ion mobility ..

Formation of nitrosamines and alkyldiazohydroxides in the gas phase: The CH3NH NO reaction revisited

G Da Silva

2013-07-16

Aminyl free radicals of the form RN^•H are formed in the photochemical oxidation of primary amines, and their reaction w..

On the separation of timescales in chemically activated reactions

SJ Pinches, G Da Silva

2013-06-01

Chemically activated reactions are important in describing the composition of reactive gases including flames, planetary atmospher..

Using distonic radical ions to probe the chemistry of key combustion intermediates: The case of the benzoxyl radical anion

C Li, AKY Lam, GN Khairallah, JM White, RAJ O'Hair, G Da Silva

2013-04-01

The benzoxyl radical is a key intermediate in the combustion of toluene and other aromatic hydrocarbons, yet relatively little exp..

G3X-K theory: A composite theoretical method for thermochemical kinetics

G Da Silva

2013-02-12

A composite theoretical method for accurate thermochemical kinetics, G3X-K, is described. This method is accurate to around 0.5 kc..

Atmospheric chemistry of 2-aminoethanol (MEA): Reaction of the NH 2•CHCH2OH radical with O2

G Da Silva

2012-11-15

The alkanolamine 2-aminoethanol (NH<inf>2</inf>CH<inf>2</inf>CH <inf>2</inf>OH), otherwise known as monoethanolamine (MEA), is a w..

Reaction of methacrolein with the hydroxyl radical in air: Incorporation of secondary O 2 addition into the MACR OH master equation

G Da Silva

2012-06-07

Methacrolein (MACR) plays an important role in atmospheric chemistry within the planetary boundary layer, as it is one of the majo..

Concerted HO 2 elimination from α-aminoalkylperoxyl free radicals: Experimental and theoretical evidence from the gas-phase NH 2 •CHCO 2 - O 2 reaction

G Da Silva, BB Kirk, C Lloyd, AJ Trevitt, SJ Blanksby

2012-04-05

We have investigated the gas-phase reaction of the α-aminoacetate (glycyl) radical anion (NH <inf>2</inf> ^•CHCO <inf>2<..

Gas-phase reactions of aryl radicals with 2-butyne: Experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation

AKY Lam, C Li, G Khairallah, BB Kirk, SJ Blanksby, AJ Trevitt, U Wille, RAJ O'Hair, G Da Silva

2012-02-21

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated ..

Reactions of simple and peptidic alpha-carboxylate radical anions with dioxygen in the gas phase

T Ly, BB Kirk, PI Hettiarachchi, BLJ Poad, AJ Trevitt, G Da Silva, SJ Blanksby

2011-09-28

α-Carboxylate radical anions are potential reactive intermediates in the free radical oxidation of biological molecules (e.g., fat..