Hydration of OCS with one to four water molecules in atmospheric and laboratory conditions.
Hydration of OCS with one to four water molecules in atmospheric and laboratory conditions.
复制标题
DOI：
10.1021/jp800229k
复制
发表时间：
2008-04
期刊：
影响因子：
--
通讯作者：
G. M. Hartt;G. Shields;K. Kirschner
中科院分区：
文献类型：
--
作者：
G. M. Hartt;G. Shields;K. Kirschner
羰基硫是大气中最丰富的含硫气体。我们用MP2和CCSD（T）理论研究了羰基硫与1 ~ 4个水分子相互作用的结构和热化学。我们已经完成了对OCS（H2O）n簇的广泛搜索，其中n = 1-4。我们用MP2/aug-cc-pVDZ方法定位了3个二聚体、2个三聚体、5个四聚体和4个五聚体。在每一个与两个或两个以上的沃茨的复合物，OCS优先与低能量的水簇相互作用。我们的研究结果符合目前的理论和实验文献，显示与可用的OCS（H2O）物种的几何形状和频率的相关性。CCSD（T）/aug-cc-pVTZ热化学值结合对流层中OCS的平均含量和H2O的饱和浓度，得到了298 K时10（6）OCS（H2O）团簇xcm（-3）和10（2）OCS（H2O）2团簇xcm（-3）的预测值.我们预测OCS（H2O）n，n = 1-4，应占主导地位的低温分子束的结构，并确定特定的红外振动，可用于识别这些不同的集群。
Carbonyl sulfide is the most abundant sulfur gas in the atmosphere. We have used MP2 and CCSD(T) theory to study the structures and thermochemistries of carbonyl sulfide interacting with one to four water molecules. We have completed an extensive search for clusters of OCS(H2O)n , where n = 1-4. We located three dimers, two trimers, five tetramers, and four pentamers with the MP2/aug-cc-pVDZ method. In each of the complexes with two or more waters, OCS preferentially interacts with low-energy water clusters. Our results match current theoretical and experimental literature, showing correlation with available geometries and frequencies for the OCS(H2O) species. The CCSD(T)/aug-cc-pVTZ thermochemical values combined with the average amount of OCS and the saturated concentration of H2O in the troposphere, lead to the prediction of 10(6) OCS(H2O) clusters x cm(-3) and 10(2) OCS(H2O)2 clusters x cm(-3) at 298 K. We predict the structures of OCS(H2O)n , n = 1-4 that should predominate in a low-temperature molecular beam and identify specific infrared vibrations that can be used to identify these different clusters.