Negative Ion Photoelectron Spectroscopy Reveals Thermodynamic Advantage of Organic Acids in Facilitating Formation of Bisulfate Ion Clusters: Atmospheric Implications

Hou, Gao‐Lei; Lin, Wei; Deng, S. H. M.; Zhang, Jian; Zheng, Wei; Paesani, Francesco; Wang, Xue‐Bin

doi:10.1021/jz400108y

Cited by 57 publications

(98 citation statements)

References 67 publications

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“…However, as for the water molecule introduced into the reaction, when the typical concentration is about 5.18 × 10 17 molecule cm −3 . the corresponding rate ratio is about 11 at 240 K. Therefore, the NH 2 + H 2 SO 4 … H 2 O reaction can complete well with the naked NH 2 + H 2 SO 4 reaction at temperatures below 240 K. The formed HSO 4 … NH 3 complex furthermore interacts with atmospheric molecules, which are involved in ion‐mediated nucleation …”

Section: Resultsmentioning

confidence: 99%

Theoretical Studies on Reactions of OH with H₂SO₄^…NH₃Complex and NH₂with H₂SO₄in the Presence of Water

et al. 2016

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The OH + H 2 SO 4 … NH 3 , NH 2 + H 2 SO 4 , and NH 2 + H 2 SO 4 … H 2 O reactions have been theoretically investigated using high-accuracy quantum chemical methods and conventional transition state theory. The calculation results reveal that remarkable tunneling effects appear at 200 K in the OH + H 2 SO 4 … NH 3 reaction, compared with obvious tunneling effects below 100 K in the OH + NH 3 reaction. The calculated rate constants predict that the hydrogen atom of the free OH group in M1 (H 2 SO 4 … NH 3 ) abstracted via OH can compete well with the H atom in H 2 SO 4abstracted by OH at 200-240 K. The reaction kinetic results also show that a single water molecule could play an important role in the NH 2 + H 2 SO 4 … H 2 O reaction below 240 K. The present results provide new insights into the atmospheric oxidation of sulfuric acid, which could be of great use in understanding atmospheric nucleation processes. Additionally, the findings are tunneling effects enhanced by sulfuric acid, which may be wide applications in reaction kinetics of gas-phase reactions.

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Section: Resultsmentioning

confidence: 99%

Theoretical Studies on Reactions of OH with H₂SO₄^…NH₃Complex and NH₂with H₂SO₄in the Presence of Water

et al. 2016

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“…However, sulfuric acid is not abundant enough in the atmosphere to alone explain the observed formation rates of new particles (9). It remains unclear how other compounds participate, but clusters involving sulfuric acid may be stabilized by electric charge, water vapor, bases such as ammonia and amines (9)(10)(11)(12), and oxidized organics (13)(14)(15)(16). The formation of stable clusters is a distinct critical step in atmospheric new particle formation (3).…”

Section: Significancementioning

confidence: 99%

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

Schobesberger

Junninen

Bianchi

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

328

343

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Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions. Changes to CCN number concentrations from preindustrial times constitute a major uncertainty in estimates of anthropogenic climate forcing (1). New particle formation dominates the total number concentrations of atmospheric aerosol particles; however, newly formed particles must grow from D p ∼ 1.5 to D p ∼ 50-100 nm to be able to act as CCN, and the vast majority are SignificanceThe formation of nanoparticles by condensable vapors in the atmosphere influences radiative forcing and therefore climate. We explored the detailed mechanism of particle formation, in particular the role of oxidized organic molecules that arise from the oxidation of monoterpenes, a class of volatile organic compounds emitted from plants. We mimicked atmospheric conditions in a well-controlled laboratory setup and found that these oxidized organics form initial clusters directly with single sulfuric acid molecules. The clusters then grow by the further addition of both sulfuric acid and organic molecules. Some of the organics are remarkably highly oxidized, a critical feature that enables them to participate in forming initial stable molecular clusters and to facilitate the first steps of atmospheric nanoparticle formation.

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“…Sulfuric acid has been shown to be the key compound in atmospheric particle formation (see, for example, Kuang et al 5 and Sihto et al 6 ), but is not alone able to explain the formation rates observed in the troposphere. Instead, other atmospherically relevant species, such as bases and organic compounds, as well as ions, have been proposed to enhance the formation and growth of sulfuric acid-containing particles (see, for example, Zhang et al, 7 Zhang et al, 8 and Hou et al 9 ), out of which base compounds, most importantly ammonia and amines, seem to be promising candidates to take part in the first steps of cluster formation. Ammonia and dimethylamine have been theoretically shown to be capable of stabilizing sulfuric acid clusters (Kurtén et al 10 and Loukonen et al 11 ).…”

Section: Introductionmentioning

confidence: 99%

Free energy barrier in the growth of sulfuric acid–ammonia and sulfuric acid–dimethylamine clusters

Olenius

Kupiainen-Määttä²,

Ortega³

et al. 2013

The Journal of Chemical Physics

201

339

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The first step in atmospheric new particle formation involves the aggregation of gas phase molecules into small molecular clusters that can grow by colliding with gas molecules and each other. In this work we used first principles quantum chemistry combined with a dynamic model to study the steady-state kinetics of sets of small clusters consisting of sulfuric acid and ammonia or sulfuric acid and dimethylamine molecules. Both sets were studied with and without electrically charged clusters. We show the main clustering pathways in the simulated systems together with the quantum chemical Gibbs free energies of formation of the growing clusters. In the sulfuric acid-ammonia system, the major growth pathways exhibit free energy barriers, whereas in the acid-dimethylamine system the growth occurs mainly via barrierless condensation. When ions are present, charged clusters contribute significantly to the growth in the acid-ammonia system. For dimethylamine the role of ions is minor, except at very low acid concentration, and the growing clusters are electrically neutral.

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Negative Ion Photoelectron Spectroscopy Reveals Thermodynamic Advantage of Organic Acids in Facilitating Formation of Bisulfate Ion Clusters: Atmospheric Implications

Cited by 57 publications

References 67 publications

Theoretical Studies on Reactions of OH with H₂SO₄^…NH₃Complex and NH₂with H₂SO₄in the Presence of Water

Theoretical Studies on Reactions of OH with H₂SO₄^…NH₃Complex and NH₂with H₂SO₄in the Presence of Water

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

Free energy barrier in the growth of sulfuric acid–ammonia and sulfuric acid–dimethylamine clusters

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Negative Ion Photoelectron Spectroscopy Reveals Thermodynamic Advantage of Organic Acids in Facilitating Formation of Bisulfate Ion Clusters: Atmospheric Implications

Cited by 57 publications

References 67 publications

Theoretical Studies on Reactions of OH with H2SO4…NH3Complex and NH2with H2SO4in the Presence of Water

Theoretical Studies on Reactions of OH with H2SO4…NH3Complex and NH2with H2SO4in the Presence of Water

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

Free energy barrier in the growth of sulfuric acid–ammonia and sulfuric acid–dimethylamine clusters

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Theoretical Studies on Reactions of OH with H₂SO₄^…NH₃Complex and NH₂with H₂SO₄in the Presence of Water

Theoretical Studies on Reactions of OH with H₂SO₄^…NH₃Complex and NH₂with H₂SO₄in the Presence of Water