| Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications. | |
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MedLine Citation:
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PMID: 22296037 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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The role of the binary nucleation of sulfuric acid and water to form aerosols 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=1-6, we used a scheme combining molecular dynamics 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 RI-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 ionic 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 were favorable at colder regions of the troposphere (T = 216.65 - 273.15 K) for n=1-6, but the formation of clusters with n ≥ 5 is not favorable at higher (T > 273.15K) temperatures. Our results suggest the critical cluster of a binary H2SO4-H2O system must contain more than one H2SO4 and are in concert with recent findings1 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 nucleation of sulfuric acid and water cannot account for nucleation of sulfuric acid in the lower troposphere. |
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Authors:
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Berhane Temelso; Thomas E Morrell; Robert M Shields; Marco A Allodi; Elena K Wood; Karl N Kirschner; Thomas C Castonguay; Kaye A Archer; George C Shields |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-2-1 |
Journal Detail:
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Title: The journal of physical chemistry. A Volume: - ISSN: 1520-5215 ISO Abbreviation: - Publication Date: 2012 Feb |
Date Detail:
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Created Date: 2012-2-2 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9890903 Medline TA: J Phys Chem A Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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