Ultrafast dynamics of acetone–water clusters: the influence of solvation

Hurley, S. M.; Dermota, T. E.; Hydutsky, D. P.; Castleman, A. W.

doi:10.1016/s1387-3806(03)00218-5

Cited by 12 publications

(8 citation statements)

References 38 publications

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“…Due to a possible direct acetone photolysis, both the methylperoxy radical and the acetylperoxy radical can be formed by reactions R-21–R-23. The contribution of the cross reaction of the acetonylperoxy radical with these two radicals is small because the low quantum yield of the acetone photolysis is Φ = 0.061 at Φ = 270 nm or Φ = 0.053 for the wavelength range 200–300 nm. , The obtained peroxy radical concentration from the photolysis of acetone is about 9.7 × 10 –8 M for both acetylperoxy and methylperoxy radicals corresponding to about 16% of the initial acetonylperoxy radical concentration.…”

Section: Resultsmentioning

confidence: 97%

Laboratory Kinetic and Mechanistic Studies on the OH-Initiated Oxidation of Acetone in Aqueous Solution

et al. 2012

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The OH-initiated oxidation of acetone in aqueous solution is investigated because of its potential implications in atmospheric chemistry. The UV-spectrum of the transient acetonylperoxy radical was measured. Two characteristic absorption bands of the acetonylperoxy radical spectrum are found in the 220-400 nm wavelength region. The rate constant for the recombination reaction of the acetonylperoxy radical was determined as a function of temperature for the first time in aqueous solution with k(rec,298 K) = (7.3 ± 1.3) × 10(8) M(-1) s(-1), E(A) = 4.5 ± 3.3 kJ mol(-1), and A = (4.7 ± 2.7) × 10(9) M(-1) s(-1). Furthermore, kinetic investigations of the OH-initiated oxidation of methylglyoxal and pyruvic acid were performed with the following results: for methylglyoxal, k(second) = (6.2 ± 0.2) × 10(8) M(-1) s(-1), E(A) = 12 ± 2 kJ mol(-1), and A = (7.8 ± 0.2) × 10(9) M(-1) s(-1); for pyruvic acid (pH = 0), k(second) = (3.2 ± 0.6) × 10(8) M(-1) s(-1), E(A) = 15 ± 5 kJ mol(-1), and A = (1.1 ± 0.1) × 10(11) M(-1) s(-1); for pyruvate (pH = 6), k(second) = (7.1 ± 2.4) × 10(8) M(-1) s(-1), E(A) = 25 ± 19 kJ mol(-1), and A = (1.5 ± 0.4) × 10(13) M(-1) s(-1). Quantitative product studies were done as a function of the number of laser photolysis pulses for acetone and its oxidation products methylglyoxal, hydroxyacetone, pyruvic acid, acetic acid, and oxalic acid. After the recombination reaction of acetonylperoxy radicals, there are two possible decomposition reactions where the primary products methylglyoxal and hydroxyacetone are formed. From product analysis after a single photolysis laser shot, the ratio of the main product-forming reactions was determined as (A) 30% and (B) 56% for the methylglyoxal formation via channel A to yield two molecules of methylglyoxal and channel B to yield one molecule of methylglyoxal and one molecule of hydroxyacetone. The remaining product can be ascribed to channel C, the radical-retaining channel forming alkoxy radicals with a yield of 14%. Pyruvic acid and acetic acid were found to be the major intermediates estimated with concentrations in the same order of magnitude and a similar time profile, indicating that acetic acid is also a possible oxidation product of methylglyoxal.

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Section: Resultsmentioning

confidence: 97%

Laboratory Kinetic and Mechanistic Studies on the OH-Initiated Oxidation of Acetone in Aqueous Solution

et al. 2012

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“…We just mention here a few. Clusters of pure acetone have been studied by Buzza et al (1996a) and Buzza et al (1996b), mixed cluster of acetone and water, for example, by Hurley et al (2003).…”

Section: Water-and Other Hydrogen-bonded-clustersmentioning

confidence: 99%

Ultrafast dynamics in isolated molecules and molecular clusters

2006

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During the past decade the understanding of photo-induced ultrafast dynamics in molecular systems has improved at an unforeseen speed and a wealth of detailed insight into the fundamental processes has been obtained. This review summarizes our present knowledge on ultrafast dynamics in isolated molecules and molecular clusters evolving after excitation with femtosecond pulses as studied by pump-probe analysis in real time. Experimental tools and methods as well as theoretical models are described which have been developed to glean information on primary, ultrafast processes in photophysics, photochemistry and photobiology. The relevant processes are explained by way of example-from wave packet dynamics in systems with a few atoms all the way to internal conversion via conical intersections in bio-chromophores. A systematic overview on characteristic systems follows, starting with diatomic and including larger organic molecules as well as various types of molecular clusters, such as micro-solvated chromophore molecules. For conciseness the focus is on molecular systems which remain unperturbed by the laser pulses-apart from the excitation and detection processes as such. Thus, only some aspects of controlling and manipulating molecular reactions by shaped and/or very intense laser pulses are discussed briefly for particularly instructive examples, illustrating the perspectives of this prospering field. The material presented in this review comprises some prototypical examples from earlier pioneering work but emphasizes studies from recent years and covers the most important and latest developments until January 2006.

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“…In particular, reactions of acetone with polar molecules have attracted considerable attention since they provide an alternative route to understand the most fundamental reaction mechanisms such as hydration, ketal formation and imine formation [11][12][13]. Many studies have been conducted for the heteroclusters of acetone with polar molecules, such as ammonia and water [14][15][16][17][18][19][20]. Observation of magic numbers for these cluster ions due to the optimization of hydrogen-bonding has been the primary focus.…”

Section: Introductionmentioning

confidence: 99%