Quantitative Infrared Intensity Studies of Vapor-Phase Glyoxal, Methylglyoxal, and 2,3-Butanedione (Diacetyl) with Vibrational Assignments

Profeta, Luisa T. M.; Sams, Robert L.; Johnson, Timothy J.; Williams, Stephen D.

doi:10.1021/jp204532x

Cited by 52 publications

(70 citation statements)

References 113 publications

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“…24,25 Comparison between values of ∆ exp and ∆ th (Table 2) generally provides no clear tendency. Theoretical shifts derived from MP2/AVTZ frequency calculations give too large uncertainties which make doubtful any assignment when ∆ exp is smaller than 10 cm -1 .…”

Section: H 2 O Fundamentalsmentioning

confidence: 97%

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

et al. 2016

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The complexes of diacetyl with water have been studied experimentally by Fourier transform infrared (FTIR) spectroscopy coupled to solid neon matrix and supersonic jet, and anharmonic ab initio calculations. The vibrational analysis of neon matrix spectra over the 100-7500 cm -1 infrared range confirms the existence of two nearly isoenergetic one-to-one(1/1) diacetyl-water S 1 and S 2 isomers already evidenced in a previous argon matrix study. A third form (S 3 ) predicted slightly less stable [D. Dargent et al. , J. Mol. Mod. 21, 214 (2015)] is not observed. The correct agreement obtained between neon matrix and anharmonic calculated vibrational frequencies is exploited in several cases to derive band assignments for the vibrational modes of a specific isomer. Thereafter, theoretical x ij anharmonic coupling constants are used for the attribution of combination bands and overtones relative to the 1/1 dimer. Finally, the most stable isomer of the one-to-two (1/2) diacetyl-water complex is identified in the OH stretching region of water on the grounds of comparison of experimental and calculated vibrational shifts between water dimer and the three most stable 1/2 isomers. I -IntroductionIt is now well established that non-covalent interactions such as hydrogen bonds involved in small hydrated clusters play an essential role in atmospheric chemistry, astrophysics and also in many biochemical and catalytic processes.1 Since the pioneering spectroscopic works about the enthalpy and the hydrogen bridges in crystallographic structures such as ice and liquid water, 2,3 many advanced experimental methods were developed in the last thirty years to interpret the bulk water structure and dynamics. In this context, the spectroscopic study of small water clusters produced at very low temperature in nearly isolated conditions proved to be determinant for improving the building of reliable intermolecular potential energy surfaces based on a back and forth procedure between experiment and theory. As a first step toward this objective, we can cite the challenging studies based on jet-cooled far-and near-IR laser and microwave spectroscopy which yielded new insights into the tunneling motions of the water dimer 4-6 and allowed to determine a polarisable water pair potential. 7The huge capacity of water to establish hydrogen bonds with the close environment owing to its twice role of hydrogen-bond donor and acceptor would suggest to use a molecular approach based on a step by step increase of the size of hydrates for most studies related to the hydration process of organic species. It has been shown in many previous solid 8 and gas phase studies 9-11 that very different structural architectures of hydrated organic In the following we reported a series of experiments mainly achieved in solid neon and at a least degree in the supersonic expansion of the Jet-AILES facility on the infrared beamline of the SOLEIL synchrotron. Previous studies realized in our group about the characterization of small hydrated complexes highlight...

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Section: H 2 O Fundamentalsmentioning

confidence: 97%

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

et al. 2016

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“…The photolysis rate parameterisations used in MCMv3.2 (Saunders et al, 2003) have been adjusted to replicate the photolytic conditions inside the EUPHORE chamber using measured values of j (NO 2 ). More details on the chamber modelling approach used can be found in Rickard et al (2010).…”

Section: Euphore Isoprene Photo-oxidation Experimentsmentioning

confidence: 99%

“…Longer storage times were found to have no significant effect on the GC-MS signal responses of GLY and MGLY drivatives even after 24 h storage. Since the PFBHA derivatisation process is effectively a nucleophilic addition reaction the simple steric structures and electron configurations of GLY and MGLY are favourable to the faster reaction rate (Temime et al, 2007;Reisen et al, 2003). The derivatisation process occurring in the microreactor is considered sufficiently fast that it can be used for near real-time measurement of α-dicarbonyls with the microreactor effluent passed directly for in situ GC-MS analysis.…”

Section: Optimisations Of Pfbha Concentration Reaction Temperature Amentioning

confidence: 99%

“…In recent years several different optical/spectroscopic approaches have been proposed for atmospheric measurement of α-dicarbonyls including Differential Optical Absorption Spectroscopy (DOAS) (Volkamer et al, 2005a;MacDonald et al, 2012), Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS) (Thalman and Volkamer, 2010;Washenfelder et al, 2008), Laser-Induced Phosphorescence (LIP) Spectrometry (Henry et al, 2012), and Fourier Transform InfraRed (FTIR) absorption spectroscopy (Connelly et al, 2012;Profeta et al, 2012). DOAS is a wellestablished technique used to identify trace gases by means of their individual differential (i.e.…”

Section: Introductionmentioning

confidence: 99%

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A smog chamber comparison of a microfluidic derivatisation measurement of gas-phase glyoxal and methylglyoxal with other analytical techniques

et al. 2014

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Abstract.A microfluidic lab-on-a-chip derivatisation technique has been developed to measure part per billion (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method is compared with other techniques in a smog chamber experiment. The method uses o-(2, 3, 4, 5, 6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatisation reagent and a microfabricated planar glass micro-reactor comprising an inlet, gas and fluid splitting and combining channels, mixing junctions, and a heated capillary reaction microchannel. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the micro-reactor resulted in a fast and highly efficient derivatisation reaction, generating an effluent stream ready for direct introduction to a gas chromatograph-mass spectrometer (GC-MS). A linear response for GLY was observed over a calibration range 0.7 to 400 ppbV, and for MGLY of 1.2 to 300 ppbV, when derivatised under optimal reaction conditions. The analytical performance shows good accuracy (6.6 % for GLY and 7.5 % for MGLY), suitable precision (<12.0 %) with method detection limits (MDLs) of 75 pptV for GLY and 185 pptV for MGLY, with a time resolution of 30 min. These MDLs are below or close to typical concentrations of these compounds observed in ambient air. The feasibility of the technique was assessed by applying the methodology to quantify α-dicarbonyls formed during the photo-oxidation of isoprene in the EUPHORE chamber. Good correlations were found between microfluidic measurements and Fourier Transform InfraRed spectroscopy (FTIR) with a correlation coefficient (r 2 ) of 0.84, Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS) (r 2 = 0.75), solid phase micro extraction (SPME) (r 2 = 0.89), and a photochemical chamber box modelling calculation (r 2 = 0.79) for GLY measurements. For MGLY measurements, the microfluidic technique showed good agreement with BBCEAS (r 2 = 0.87), SPME (r 2 = 0.76), and the modeling simulation (r 2 = 0.83), FTIR (r 2 = 0.72) but displayed a discrepancy with Proton-Transfer Reaction Timeof-Flight Mass Spectrometry (PTR-ToF-MS) with r 2 value of 0.39. Published by Copernicus

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“…Recent studies have included quantitative band strengths of HNCO , H 2 O 2 (Johnson et al, 2009), and glycolaldehyde , as well as the dicarbonyls glyoxal, methylglyoxal, and diacetyl (Profeta et al, 2011). The availability of the quantitative band strengths allows evaluation programs such as MALT (Multiple Atmospheric Layer Transmission) (Griffith, 1996) to extract the mixing ratios and, ultimately, the emission factors (EFs, grams of effluent per kilogram of fuel) of biomass burning effluents; using the quantitative absorption cross-section information in the database and field measurements from either airborne or land-based systems, the EFs of dozens of species have been extracted in laboratory burns , as well as from prescribed fires in the US southwest ) and the US southeast (Burling et al, 2011;Akagi et al, 2013), including using open-path FTIR systems (Akagi et al, 2014).…”

Section: S Brauer Et Al: Isoprene Cross Sectionsmentioning

confidence: 99%

Quantitative infrared absorption cross sections of isoprene for atmospheric measurements

et al. 2014

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Abstract. Isoprene (C 5 H 8 , 2-methyl-1,3-butadiene) is a volatile organic compound (VOC) and is one of the primary contributors to annual global VOC emissions. Isoprene is produced primarily by vegetation as well as anthropogenic sources, and its OH-and O 3 -initiated oxidations are a major source of atmospheric oxygenated organics. Few quantitative infrared studies have been reported for isoprene, limiting the ability to quantify isoprene emissions via remote or in situ infrared detection. We thus report absorption cross sections and integrated band intensities for isoprene in the 600-6500 cm −1 region. The pressure-broadened (1 atmosphere N 2 ) spectra were recorded at 278, 298, and 323 K in a 19.94 cm path-length cell at 0.112 cm −1 resolution, using a Bruker IFS 66v/S Fourier transform infrared (FTIR) spectrometer. Composite spectra are derived from a minimum of seven isoprene sample pressures, each at one of three temperatures, and the number densities are normalized to 296 K and 1 atm.

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Quantitative Infrared Intensity Studies of Vapor-Phase Glyoxal, Methylglyoxal, and 2,3-Butanedione (Diacetyl) with Vibrational Assignments

Cited by 52 publications

References 113 publications

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

A smog chamber comparison of a microfluidic derivatisation measurement of gas-phase glyoxal and methylglyoxal with other analytical techniques

Quantitative infrared absorption cross sections of isoprene for atmospheric measurements

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