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Direct Link between Structure and Hydration in Ammonium and Aminium Bisulfate Clusters Implicated in Atmospheric New Particle Formation.
Journal of Physical Chemistry Letters 2018 September 21
The acid-base chemistry of amines and sulfuric acid promotes growth in the early stages of atmospheric new particle formation, with more basic amines enhancing growth rates. Hydration of these particles has been proposed to depend on acidity or basicity but is difficult to quantify; therefore, the role of water in this process is not well understood. Using tandem mass spectrometry coupled to a temperature-controlled ion trap, we show that water uptake by aminium bisulfate clusters depends on the total number of free hydrogen bond donors in the cluster and is unaffected by the interchange of amines featuring the same number of substituents but differing gas-phase basicity. Analyzing this trend reveals site-specific propensities for hydration. These results indicate that hydration is determined by structural factors and that reported dependences on acidity or basicity arise from the weaker correlation between the number of hydrogen bond donors of amines and their gas-phase basicity.
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