Elm, Jonas5; Kurtén, Theo3; Bilde, Merete4; Mikkelsen, Kurt Valentin6
1 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet2 Department of Chemistry, Faculty of Science, Københavns Universitet3 University of Helsinki4 Institut for Kemi, Aarhus Universitet5 Department of Chemistry, Faculty of Science, Københavns Universitet6 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet
exploring the thermodynamic landscape of cluster growth
We investigate the molecular interactions between the semivolatile α-pinene oxidation product pinic acid and sulfuric acid using computational methods. The stepwise Gibbs free energies of formation have been calculated utilizing the M06-2X functional, and the stability of the clusters is evaluated from the corresponding ΔG values. The first two additions of sulfuric acid to pinic acid are found to be favorable with ΔG values of -9.06 and -10.41 kcal/mol. Addition of a third sulfuric acid molecule is less favorable and leads to a structural rearrangement forming a bridged sulfuric acid-pinic acid cluster. The involvement of more than one pinic acid molecule in a single cluster is observed to lead to the formation of favorable (pinic acid)2(H2SO4) and (pinic acid)2(H2SO4)2 clusters. The identified most favorable growth paths starting from a single pinic acid molecule lead to closed structures without the further possibility for attachment of either sulfuric acid or pinic acid. This suggests that pinic acid cannot be a key species in the first steps in nucleation, but the favorable interactions between sulfuric acid and pinic acid imply that pinic acid can contribute to the subsequent growth of an existing nucleus by condensation.
Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophysical, 2014, Vol 118, Issue 36, p. 7892-900