Hydrogen-Bond Topology Is More Important Than Acid/Base Strength in Atmospheric Prenucleation Clusters
Hydrogen-Bond Topology Is More Important Than Acid/Base Strength in Atmospheric Prenucleation Clusters
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DOI：
10.1021/acs.jpca.1c10754
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发表时间：
2022-03-17
影响因子：
2.9
通讯作者：
Shields, George C.
中科院分区：
文献类型：
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作者：
Harold, Shannon E.;Bready, Conor J.;Shields, George C.
我们探索了这样一种假设，即在纳米级水平上，酸和碱可能表现出与本体溶液不同的行为。我们的研究体系由硫酸、甲酸、氨和水组成。我们在DFT几何上计算了高度精确的基于域的局部对自然轨道耦合簇/完全基组（DLPNO-CCSD（T）/CBS）能量，并使用所得的簇形成吉布斯自由能来计算每个可能簇的整体平衡常数。结合初始单体浓度的平衡常数被用来预测在对流层的顶部和底部的集群的形成。我们的研究结果表明，甲酸是有效的氨在形成簇与硫酸和水。甲酸的结构特别适合与硫酸形成氢键。此外，它可以与水合作，形成桥从硫酸的一侧到另一侧，因此证明氢键拓扑结构比酸/碱强度更重要，在这些大气prenucleation集群。
We explored the hypothesis that on the nanoscale level, acids and bases might exhibit different behavior than in bulk solution. Our study system consisted of sulfuric acid, formic acid, ammonia, and water. We calculated highly accurate Domain-based Local pair-Natural Orbital-Coupled-Cluster/Complete Basis Set (DLPNO-CCSD(T)/CBS) energies on DFT geometries and used the resulting Gibbs free energies for cluster formation to compute the overall equilibrium constants for every possible cluster. The equilibrium constants combined with the initial monomer concentrations were used to predict the formation of clusters at the top and the bottom of the troposphere. Our results show that formic acid is as effective as ammonia at forming clusters with sulfuric acid and water. The structure of formic acid is uniquely suited to form hydrogen bonds with sulfuric acid. Additionally, it can partner with water to form bridges from one side of sulfuric acid to the other, hence demonstrating that hydrogen bonding topology is more important than acid/base strength in these atmospheric prenucleation clusters.