Hydration increases the lifetime of HSO&amp;lt;sub&amp;gt;5&amp;lt;/sub&amp;gt; and enhances its ability to act as a nucleation precursor – a computational study

Kurtén, Theo; Berndt, Thorsten; Stratmann, Frank

doi:10.5194/acp-9-3357-2009

Cited by 19 publications

(28 citation statements)

References 46 publications

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“…Its features have been reported and discussed recently by Solimannejad and co-workers 30 and our results, regarding the optimized geometries and energies, compare quite well with previous works in the literature. 30,63 It is only worth pointing out here that, as it has been shown by Solimannejad and co-workers, 30 the AIM analysis at the bcp of the SÁ Á ÁO(OH) interaction presents features of weak interaction character (the topological values are r = 0.0653, r 2 r = 0.1156, and H = À0.0100 a.u.). This complex has C s symmetry ( 2 A 0 0 electronic state) and the unpaired electron is mainly located on the OO group of the hydroperoxyl radical moiety, in a plane perpendicular to the SO 3 plane, so that it does not participate in the interaction between the HO 2 and SO 3 moieties.…”

Section: Technical Details Of the Calculationssupporting

confidence: 52%

The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

González

Torrent‐Sucarrat

Anglada

2010

Phys. Chem. Chem. Phys.

111

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The influence of a single water molecule on the gas-phase reactivity of the HO(2) radical has been investigated by studying the reactions of SO(3) with the HO(2) radical and with the H(2)O...HO(2) radical complex. The naked reaction leads to the formation of the HSO(5) radical, with a computed binding energy of 13.81 kcal mol(-1). The reaction with the H(2)O...HO(2) radical complex can give two different products, namely (a) HSO(5) + H(2)O, which has a binding energy that is computed to be 4.76 kcal mol(-1) more stable than the SO(3) + H(2)O...HO(2) reactants (Delta(E + ZPE) at 0K) and an estimated branching ratio of about 34% at 298K and (b) sulfuric acid and the hydroperoxyl radical, which is computed to be 10.51 kcal mol(-1) below the energy of the reactants (Delta(E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H(2)SO(4) may have relevance in the chemistry of the atmosphere. Interestingly, the water molecule acts as a catalyst, [as it occurs in (a)] or as a reactant [as it occurs in (b)]. For a sake of completeness we have also calculated the anharmonic vibrational frequencies for HO(2), HSO(5), the HSO(5)...H(2)O hydrogen bonded complex, H(2)SO(4), and two H(2)SO(4)...H(2)O complexes, in order to help with the possible experimental identification of some of these species.

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Section: Technical Details Of the Calculationssupporting

confidence: 52%

The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

González

Torrent‐Sucarrat

Anglada

2010

Phys. Chem. Chem. Phys.

111

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“…In order to distinguish between sunny and cloudy conditions, the cloud cover was estimated with the clear sky index (CSI) described by Marty and Philipona (2000). The CSI is defined as the ratio between the apparent emittance and the theoretical clear sky apparent emittance and is calculated from the atmospheric long-wave radiation, air temperature, and relative humidity.…”

Section: Determination Of Cloud Coveragementioning

confidence: 99%

Chemical characterization of atmospheric ions at the high altitude research station Jungfraujoch (Switzerland)

et al. 2017

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Abstract. The ion composition at high altitude (3454 m a.s.l.) was measured with an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) during a period of 9 months, from August 2013 to April 2014. The negative mass spectra were dominated by the ions of sulfuric, nitric, malonic, and methanesulfonic acid (MSA) as well as SO5−. The most prominent positive ion peaks were from amines. The other cations were mainly organic compounds clustered with a nitrogen-containing ion, which could be either NH4+ or an aminium. Occasionally the positive spectra were characterized by groups of compounds each differing by a methylene group. In the negative spectrum, sulfuric acid was always observed during clear sky conditions following the diurnal cycle of solar irradiation. On many occasions we also saw a high signal of sulfuric acid during nighttime when clusters up to the tetramer were observed. A plausible reason for these events could be evaporation from particles at low relative humidity. A remarkably strong correlation between the signals of SO5− and CH3SO3− was observed for the full measurement period. The presence of these two ions during both the day and the night suggests a non-photochemical channel of formation which is possibly linked to halogen chemistry. Halogenated species, especially Br− and IO3−, were frequently observed in air masses that originated mainly from the Atlantic Ocean and occasionally from continental areas based on back trajectory analyses. We found I2O5 clustered with an ion, a species that was proposed from laboratory and modeling studies. All halogenated ions exhibited an unexpected diurnal behavior with low values during daytime. New particle formation (NPF) events were observed and characterized by (1) highly oxygenated molecules (HOMs) and low sulfuric acid or (2) ammonia–sulfuric acid clusters. We present characteristic spectra for each of these two event types based on 26 nucleation episodes. The mass spectrum of the ammonia–sulfuric acid nucleation event compares very well with laboratory measurements reported from the CLOUD chamber. A source receptor analysis indicates that NPF events at the Jungfraujoch take place within a restricted period of time of 24–48 h after air masses have had contact with the boundary layer. This time frame appears to be crucial to reach an optimal oxidation state and concentration of organic molecules necessary to facilitate nucleation.

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“…Eisele, 1989b;Eisele et al, 2006), but to our knowledge the only previous atmospheric observations of the SO − 5 ion was by Junninen et al (2010). Model studies on the role of HSO 5 in the nucleation process has also been performed by Kurtén et al (2009), and this metastable radical has been found to be significantly stabilized by hydration, i.e. by forming clusters with water molecules, in ambient conditions.…”

Section: Negative Spectramentioning

confidence: 99%

Composition and temporal behavior of ambient ions in the boreal forest

et al. 2010

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A recently developed atmospheric pressure interface mass spectrometer (APi-TOF) measured the negative and positive ambient ion composition at a boreal forest site. As observed in previous studies, the negative ions were dominated by strong organic and inorganic acids (e.g. malonic, nitric and sulfuric acid), whereas the positive ions consisted of strong bases (e.g. alkyl pyridines and quinolines). Several new ions and clusters of ions were identified based on their exact masses, made possible by the high resolution, mass accuracy and sensitivity of the APi-TOF. Time series correlograms aided in peak identification and assigning the atomic compositions to molecules. Quantum chemical calculations of proton affinities and cluster stabilities were also used to confirm the plausibility of the assignments. Acids in the gas phase are predominantly formed by oxidation in the gas phase, and thus the concentrations are expected to vary strongly between day and night. This was also the case in this study, where the negative ions showed strong diurnal behavior, whereas the daily changes in the positive ions were considerably smaller. A special focus in this work was the changes in the ion distributions occurring during new particle formation events. We found that sulfuric acid, together with its clusters, dominated the negative ion spectrum during these events. The monomer (HSO4−) was the largest peak, together with the dimer (H2SO4 · HSO4−) and trimer ((H2SO4)2 · HSO4−). SO5− also tracked HSO4− at around 20% of the HSO4− concentration at all times. During the strongest events, the tetramer and a cluster with the tetramer and ammonia were also detected. Quantum chemical calculations predict that sulfuric acid clusters containing ammonia are much more stable when neutral, thus the detection of a single ion cluster implies that ammonia can be an important compound in the nucleation process. We also believe to have made the first observations of an organosulfate (glycolic acid sulfate) in the gas phase. This ion, and its cluster with sulfuric acid, correlates with the HSO4−, but peaks in the early afternoon, some hours later than HSO4− itself. A list of all identified ions is presented in the supplementary material, and also a list of all detected masses not yet identified

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Hydration increases the lifetime of HSO<sub>5</sub> and enhances its ability to act as a nucleation precursor – a computational study

Cited by 19 publications

References 46 publications

The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

Chemical characterization of atmospheric ions at the high altitude research station Jungfraujoch (Switzerland)

Composition and temporal behavior of ambient ions in the boreal forest

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