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Quantum mechanical study of sulfuric acid hydration: Atmospheric implications

 
: Temelso, B.; Morrell, T.E.; Shields, R.M.; Allodi, M.A.; Wood, E.K.; Kirschner, K.N.; Castonguay, T.C.; Archer, K.A.; Shields, G.C.

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Journal of physical chemistry. A 116 (2012), Nr.9, S.2209-2224
ISSN: 1089-5639
Englisch
Zeitschriftenaufsatz
Fraunhofer SCAI ()

Abstract
The role of the binary nucleation of sulfuric acid in aerosol formation and its implications for global warming is one of the fundamental unsettled questions in atmospheric chemistry. We have investigated the thermodynamics of sulfuric acid hydration using ab initio quantum mechanical methods. For H2SO4(H2O)n where n = 16, we used a scheme combining molecular dynamics configurational sampling with high-level ab initio calculations to locate the global and many low lying local minima for each cluster size. For each isomer, we extrapolated the MøllerPlesset perturbation theory (MP2) energies to their complete basis set (CBS) limit and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled harmonic vibrational frequencies. We found that ion ic pair (HSO4·H3O+)(H2O)n-1 clusters are competitive with the neutral (H2SO4)(H2O)n clusters for n ≥ 3 and are more stable than neutral clusters for n ≥ 4 depending on the temperature. The Boltzmann averaged Gibbs free energies for the formation of H2SO4(H2O)n clusters are favorable in colder regions of the troposphere (T = 216.65273.15 K) for n = 16, but the formation of clusters with n ≥ 5 is not favorable at higher (T > 273.15 K) temperatures. Our results suggest the critical cluster of a binary H2SO4H2O system must contain more than one H2SO4 and are in concert with recent findings(1) that the role of binary nucleation is small at ambient conditions, but significant at colder regions of the troposphere. Overall, the results support the idea that binary nucle ation of sulfuric acid and water cannot account for nucleation of sulfuric acid in the lower troposphere.

: http://publica.fraunhofer.de/dokumente/N-199363.html