25 research outputs found
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>&minus;</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>&bull;H<sub>2</sub>SO<sub>4</sub>, while most amine-HSO<sub>4</sub><sup>&minus;</sup> complexes are only somewhat more strongly bound than NH<sub>3</sub>&bull;HSO<sub>4</sub><sup>&minus;</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>&minus;</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
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On the formation of sulphuric acid – Amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation
Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4)
Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere
4 pages 359-363 in the print version, additional 7 pages online.Peer reviewe
Insight into Acid–Base Nucleation Experiments by Comparison of the Chemical Composition of Positive, Negative, and Neutral Clusters
Seasonal characteristics of tropical marine boundary layer air measured at the Cape Verde Atmospheric Observatory
Atmospheric Cluster Dynamics Code: a flexible method for solution of the birth-death equations
The Atmospheric Cluster Dynamics Code (ACDC) is presented and explored. This program was created to study the first steps of atmospheric new particle formation by examining the formation of molecular clusters from atmospherically relevant molecules. The program models the cluster kinetics by explicit solution of the birth–death equations, using an efficient computer script for their generation and the MATLAB ode15s routine for their solution. Through the use of evaporation rate coefficients derived from formation free energies calculated by quantum chemical methods for clusters containing dimethylamine or ammonia and sulphuric acid, we have explored the effect of changing various parameters at atmospherically relevant monomer concentrations. We have included in our model clusters with 0–4 base molecules and 0–4 sulfuric acid molecules for which we have commensurable quantum chemical data. The tests demonstrate that large effects can be seen for even small changes in different parameters, due to the non-linearity of the system. In particular, the temperature and sticking probabilities both have a large impact on all clusters, while the boundary effects (allowing clusters to grow to sizes beyond the largest cluster that the code keeps track of, or forbidding such processes), coagulation sink terms, non-monomer collisions, and monomer concentrations can all have significant effects. Removal of coagulation sink terms prevented the system from reaching the steady state when all the initial cluster concentrations were set to the default value of 1 m[−3], which is probably an effect caused by studying only relatively small cluster sizes
From quantum chemical formation free energies to evaporation rates
Atmospheric new particle formation is an important source of atmospheric aerosols. Large efforts have been made during the past few years to identify which molecules are behind this phenomenon, but the actual birth mechanism of the particles is not yet well known. Quantum chemical calculations have proven to be a powerful tool to gain new insights into the very first steps of particle formation. In the present study we use formation free energies calculated by quantum chemical methods to estimate the evaporation rates of species from sulfuric acid clusters containing ammonia or dimethylamine. We have found that dimethylamine forms much more stable clusters with sulphuric acid than ammonia does. On the other hand, the existence of a very deep local minimum for clusters with two sulfuric acid molecules and two dimethylamine molecules hinders their growth to larger clusters. These results indicate that other compounds may be needed to make clusters grow to larger sizes (containing more than three sulfuric acid molecules)
Corrigendum to "From quantum chemical formation free energies to evaporation rates" published in Atmos. Chem. Phys., 12, 225–235, 2012
No abstract available
On the formation of sulphuric acid – amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation
Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (<i>J</i><sub>A2B2</sub>) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H<sub>2</sub>SO<sub>4</sub>]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates <i>J</i><sub>A2B2</sub> were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients <i>K</i><sub>A2B2</sub> connecting the cluster formation rate and sulphuric acid concentrations as <i>J</i><sub>A2B2</sub>=<i>K</i><sub>A2B2</sub>[H<sub>2</sub>SO<sub>4</sub>]<sup>2</sup> turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients <i>K</i><sub>A2B2</sub> with the corresponding coefficients calculated from the atmospheric observations (<i>K</i><sub>obs</sub>) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of <i>J</i><sub>A2B2</sub> as a function of [H<sub>2</sub>SO<sub>4</sub>], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient <i>K</i><sub>obs</sub> with RH and temperature agreed best with the modelled coefficient <i>K</i><sub>A2B2</sub> related to formation of a cluster with two H<sub>2</sub>SO<sub>4</sub> and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H<sub>2</sub>SO<sub>4</sub>)