Hydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study

Recent experimental findings indicate that HSO5 radicals may play a key role in the nucleation of atmospheric SO2 oxidation products. HSO5 radicals are metastable intermediates formed in the SO2 oxidation process, and their stability and lifetime are, at present, highly uncertain. Previous high-level computational studies have predicted rather low stabilities for HSO5 with respect to dissociation into SO3+HO2, and have predicted the net reaction HSO3+OH→SO3+HO2 to be slightly exothermal. However, these studies have not accounted for hydration of HSO5 or its precursor HSO3. In this study, we have estimated the effect of hydration on the stability and lifetime of HSO5 using the advanced quantum chemical methods CCSD(T) and G3B3. We have computed formation energies and free energies for mono- and dihydrates of OH, HSO3, HSO5, SO3 and HO2, and also reanalyzed the individual steps of the HSO3+O2→HSO5→SO3+HO2 reaction at a higher level of theory than previously published. Our results indicate that hydration is likely to significantly prolong the lifetime of the HSO5 intermediate in atmospheric conditions, thus increasing the probability of reactions that form products with more than one sulfur atom. Kinetic modeling indicates that these results may help explain the experimental observations that a mixture of sulfur-containing products formed from SO2 oxidation by OH radicals nucleates much more effectively than sulfuric acid taken from a liquid reservoir

Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia

We have studied the structure and formation thermodynamics of dimer clusters containing H<sub>2</sub>SO<sub>4</sub> or HSO<sub>4</sub><sup>−</sup> together with ammonia and seven different amines possibly present in the atmosphere, using the high-level ab initio methods RI-MP2 and RI-CC2. As expected from e.g. proton affinity data, the binding of all studied amine-H<sub>2</sub>SO<sub>4</sub> complexes is significantly stronger than that of NH<sub>3</sub>•H<sub>2</sub>SO<sub>4</sub>, while most amine-HSO<sub>4</sub><sup>−</sup> complexes are only somewhat more strongly bound than NH<sub>3</sub>•HSO<sub>4</sub><sup>−</sup>. Further calculations on larger cluster structures containing dimethylamine or ammonia together with two H<sub>2</sub>SO<sub>4</sub> molecules or one H<sub>2</sub>SO<sub>4</sub> molecule and one HSO<sub>4</sub><sup>−</sup> ion demonstrate that amines, unlike ammonia, significantly assist the growth of not only neutral but also ionic clusters along the H<sub>2</sub>SO<sub>4</sub> co-ordinate. A sensitivity analysis indicates that the difference in complexation free energies for amine- and ammonia-containing clusters is large enough to overcome the mass-balance effect caused by the fact that the concentration of amines in the atmosphere is probably 2 or 3 orders of magnitude lower than that of ammonia. This implies that amines might be more important than ammonia in enhancing neutral and especially ion-induced sulfuric acid-water nucleation in the atmosphere

The role of ammonia in sulfuric acid ion induced nucleation

We have developed a new multi-step strategy for quantum chemical calculations on atmospherically relevant cluster structures that makes calculation for large clusters affordable with a good accuracy-to-computational effort ratio. We have applied this strategy to evaluate the relevance of ternary ion induced nucleation; we have also performed calculations for neutral ternary nucleation for comparison. The results for neutral ternary nucleation agree with previous results, and confirm the important role of ammonia in enhancing the growth of sulfuric acid clusters. On the other hand, we have found that ammonia does not enhance the growth of ionic sulfuric acid clusters. The results also confirm that ion-induced nucleation is a barrierless process at high altitudes, but at ground level there exists a barrier due to the presence of a local minimum on the free energy surface

Proton affinities of candidates for positively charged ambient ions in boreal forests

The optimized structures and proton affinities of a total of 81 nitrogen-containing bases, chosen based on field measurements of ambient positive ions, were studied using the CBS-QB3 quantum chemical method. The results were compared to values given in the National Institute of Standards and Technology (NIST) Chemistry WebBook in cases where a value was listed. The computed values show good agreement with the values listed in NIST. Grouping the molecules based on their molecular formula, the largest calculated proton affinities for each group were also compared with experimentally observed ambient cation concentrations in a boreal forest. This comparison allows us to draw qualitative conclusions about the relative ambient concentrations of different nitrogen-containing organic base molecules

Highly oxygenated organic molecule cluster decomposition in atmospheric pressure interface time-of-flight mass spectrometers

Identification of atmospheric molecular clusters and measurement of their concentrations by atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometers may be affected by systematic error due to possible decomposition of clusters inside the instrument. Here, we perform numerical simulations of decomposition in an APi-TOF mass spectrometers and formation in the atmosphere of a set of clusters which involve a representative kind of highly oxygenated organic molecule (HOM), with the molecular formula C10H16O8. This elemental composition corresponds to one of the most common mass peaks observed in experiments on ozone-initiated autoxidation of alpha-pinene. Our results show that decomposition is highly unlikely for the considered clusters, provided their bonding energy is large enough to allow formation in the atmosphere in the first place.Peer reviewe

Corrigendum to "The role of ammonia in sulfuric acid ion induced nucleation" published in Atmos. Chem. Phys., 8, 2859–2867, 2008

No abstract available

Structures and reaction rates of the gaseous oxidation of SO₂ by an O₋₃ (H₂O)₀₋₅ cluster – a density functional theory investigation

Based on density functional theory calculations we present a study of the gaseous oxidation of SO₂ to SO₃ by an anionic O₃^&minus;(H₂O)_<i>n</i> cluster, <i>n</i> = 0–5. The configurations of the most relevant reactants, transition states, and products are discussed and compared to previous findings. Two different classes of transition states have been identified. One class is characterised by strong networks of hydrogen bonds, very similar to the reactant complexes. The other class is characterised by sparser structures of hydration water and is stabilised by high entropy. At temperatures relevant for atmospheric chemistry, the most energetically favourable class of transition states vary with the number of water molecules attached. A kinetic model is utilised, taking into account the most likely outcomes of the initial SO₂ O₃^&minus;(H₂O)_<i>n</i> collision complexes. This model shows that the reaction takes place at collision rates regardless of the number of water molecules involved. A lifetime analysis of the collision complexes supports this conclusion. Hereafter, the thermodynamics of water and O₂ condensation and evaporation from the product SO₃^&minus;O₂(H₂O)_<i>n</i> cluster is considered and the final products are predicted to be O₂SO₃^&minus; and O₂SO₃^&minus;(H₂O)₁. The low degree of hydration is rationalised through a charge analysis of the relevant complexes. Finally, the thermodynamics of a few relevant reactions of the O₂SO₃^&minus; and O₂SO₃^&minus;(H₂O)₁ complexes are considered

Ab initio studies of O2-(H2O)n and O3-(H2O)n anionic molecular clusters, n≤12

An ab initio study of gaseous clusters of O₂^&minus; and O₃^&minus; with water is presented. Based on thorough scans of configurational space, we determine the thermodynamics of cluster growth. The results are in good agreement with benchmark computational methods and existing experimental data. We find that anionic O₂^&minus;(H₂O)_<i>n</i> and O₃^&minus;(H₂O)_<i>n</i> clusters are thermally stabilized at typical atmospheric conditions for at least <i>n</i> = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H₂O is due to normal hydrogen bonding. Although clustering up to 12 H₂O, we find that the O₂ and O₃ anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O₂^&minus; and O₃^&minus; speicies are thus accessible for further reactions. We consider the distributions of cluster sizes as function of altitude before finally, the thermodynamics of a few relevant cluster reactions are considered

Rate enhancement in collisions of sulfuric acid molecules due to long-range intermolecular forces

Collisions of molecules and clusters play a key role in determining the rate of atmospheric new particle formation and growth. Traditionally the statistics of these collisions are taken from kinetic gas theory assuming spherical noninteracting particles, which may significantly underestimate the collision coefficients for most atmospherically relevant molecules. Such systematic errors in predicted new particle formation rates will also affect large-scale climate models. We studied the statistics of collisions of sulfuric acid molecules in a vacuum using atomistic molecular dynamics simulations. We found that the effective collision cross section of the H2SO4 molecule, as described by an optimized potentials for liquid simulation (OPLS). OPLS all-atom force field, is significantly larger than the hard-sphere diameter assigned to the molecule based on the liquid density of sulfuric acid. As a consequence, the actual collision coefficient is enhanced by a factor of 2.2 at 300 K compared with kinetic gas theory. This enhancement factor obtained from atomistic simulation is consistent with the discrepancy observed between experimental formation rates of clusters containing sulfuric acid and calculated formation rates using hard-sphere kinetics. We find reasonable agreement with an enhancement factor calculated from the Langevin model of capture, based on the attractive part of the atomistic intermolecular potential of mean force.Peer reviewe

Ambient sesquiterpene concentration and its link to air ion measurements

International audienceAmbient air ion size distributions have been measured continuously at the Finnish boreal forest site in Hyytiälä since spring 2003. In general, these measurements show a maximum of air ions below 1.0 nm in diameter. But this physical characterization does not provide any information about the ion's chemical composition, which is one key question regarding the explanation of nucleation events observed. In this study we propose a link of the observed maximum of negative air ions between 0.56 and 0.75 nm to the so-called stabilised Criegee biradical, formed in the reaction of biogenic sesquiterpenes with ozone and predominantly destroyed by its reaction with ambient water vapour. Calculations of the electron and proton affinities of 120 kJ mol?1 (1.24 eV) and of 960 kJ mol?1 support this link. Other possible candidates such as sulphuric acid derived clusters are unable to explain the observations made. By using this approach, we are able to calculate the ambient concentration of sesquiterpenes at the air ion instrument inlet with a high time resolution on the daily and seasonal scale. The estimated concentration is found to reveal the same seasonal pattern as emission measurements conducted at shoot level. As expected for biogenic VOCs, the concentration is obtained highest during summer (maximum values of about 100 pptv) and smallest during winter (minimum less than 1 pptv). Because of the sesquiterpenes high reactivity and its low ambient concentrations, this approach can be a first step in understanding their emission and their impact on atmospheric chemistry in more detail. The findings presented are highly relevant for emission budgets too, since boreal forests are extended over large areas of the globe