Atmospheric Significance of Water Clusters and Ozone-Water Complexes
Atmospheric Significance of Water Clusters and Ozone-Water Complexes
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DOI：
10.1021/jp407282c
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发表时间：
2013-10-10
影响因子：
2.9
通讯作者：
Francisco, Joseph S.
中科院分区：
文献类型：
--
作者：
Anglada, Josep M.;Hoffman, Gerald J.;Francisco, Joseph S.
使用 QCISD 和 CCSD(T) 方法以及 6-311G(2df,2p)、6-311+G(2df,2p)、aug-cc-pVDZ、aug-cc-pVTZ 和 aug-cc-pVQZ 基组对臭氧-水配合物 O-3 中心点中心点中心点 (H2O) (n = 1-4) 进行了理论研究外推法 达到哥伦比亚广播公司的限制。为了进行比较，水团簇 (H2O)(n) (n = 1-4) 也在相同的理论水平上进行了研究。臭氧-水复合物通过弱特定氢键和范德华相互作用的组合结合在一起。令人惊讶的是，氢键配合物不一定是最稳定的。特别是，在最稳定的 1:1 复合结构中，主要稳定因素来自范德华相互作用。计算出的结合能的高精度为讨论大气中这些团簇的丰度提供了可靠的基础。我们预测，在非常炎热和潮湿的条件下，水二聚体、三聚体和四聚体的浓度高达 9.24 x 10(15)、3.91 X 10(14) 和 2.02 X 19(14) 分子-cm(-3)，并且这些尘埃的浓度在地球大气层高度高达 10 公里的地方仍然很高。 O-3 中心点 H2O 的浓度预计比先前文献估计高出 1 到 2 个数量级：在非常炎热和潮湿的地面条件下高达 5.74 X 10(8) molecular.cm(-3)，在地球大气层高度 10 km 时高达 1.56 X 10(7) molecular.cm(-3)。其他臭氧水簇、O-3 中心点(H2O)(2)、O-3 中心点(H2O)(3) 和O-3 中心点(H2O)(4) 在大气中的浓度预计非常小，甚至可以忽略不计。
Ozone-water complexes O-3 center dot center dot center dot(H2O) (n = 1-4) have been theoretically investigated using QCISD and CCSD(T) methods along with the 6-311G(2df,2p), 6-311+G(2df,2p), aug-cc-pVDZ, aug-cc-pVTZ, and aug-cc-pVQZ basis sets and extrapolation to CBS limit. For comparison, water clusters (H2O)(n) (n = 1-4) have also been studied at the same level of theory. The ozone-water complexes are held together by a combination of weak specific hydrogen-bonding and van der Waals interactions. Surprisingly, the hydrogen-bonded complexes are not necessarily the most stable ones. In particular, in the most stable 1:1 complex structure the main stabilizing factors come from van der Waals interactions. The high accuracy of the calculated binding energies provides a reliable basis to discuss the abundance of these clusters in the atmosphere. We predict concentrations up to 9.24 x 10(15), 3.91 X 10(14), and 2.02 X 19(14) molecules-cm(-3) for water dimer, trimer, and tetramer in very hot and humid conditions and that the concentrations of these dusters would remain significant up to 10 km of altitude in the Earth's atmosphere. The concentration of O-3 center dot center dot center dot H2O is predicted to be between 1 and 2 orders of magnitude higher than previous estimation from the literature: up to 5.74 X 10(8) molecules.cm(-3) in very hot and humid conditions at ground level and up to 1.56 X 10(7) molecules.cm(-3) at 10 km of altitude of the Earth's atmosphere. The concentrations of the other ozone-water clusters, O-3 center dot center dot center dot(H2O)(2), O-3 center dot center dot center dot(H2O)(3), and O-3 center dot center dot center dot(H2O)(4) are predicted to be very small or even negligible in the atmosphere.