Binding of the atomic cations hydrogen through argon to water and hydrogen sulfide
Binding of the atomic cations hydrogen through argon to water and hydrogen sulfide
复制标题
原子阳离子氢通过氩气与水和硫化氢结合
DOI：
10.1039/c8cp05378b
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发表时间：
2018
影响因子：
3.3
通讯作者：
Fortenberry, Ryan C.
中科院分区：
文献类型：
--
作者：
Westbrook, Brent R.;Dreux, Katelyn M.;Tschumper, Gregory S.;Francisco, Joseph S.;Fortenberry, Ryan C.
水和硫化氢将与元素周期表前三行中的每一个原子阳离子结合。虽然一些原子比其他原子结合得更紧密，但显式关联的耦合团簇理论计算表明，即使对于稀有气体原子，也需要向系统注入能量才能解离这些键。最有希望的系统有浅的入射势能面(PESS)，位于不同自旋的更深的势垒之上。对于H_2O~+、H_2SS~+和H_2OS~+，这些势垒被清楚地显示出来，其中重原子键长的松弛能谱表明四重态将跨越更深束缚的双重态，从而允许相对容易的缔合，但更难解离。在寒冷和弥漫的天体物理区域，这种相互作用可能会导致新分子的形成，利用水(或硫化氢)作为更丰富的后续化学的基础。最近的工作假设氧水(H_2O)可能是彗星中分子氧形成的中间产物，这项工作至少从分子阳离子的角度支持了这一结论。
Water and hydrogen sulfide will bind with every atomic cation from the first three rows of the periodic table. While some atoms bind more tightly than others, explicitly correlated coupled cluster theory computations show that energy is required to be put into the system in order to dissociate these bonds even for noble gas atoms. The most promising systems have shallow entrance potential energy surfaces (PESs) that lie above deeper wells of a different spin. These wells are shown explicitly for H2OO+, H2SS+, and H2OS+ where relaxed PESs of the heavy atom bond lengths indicate that quartet states will cross more deeply-bound doublet states allowing for relatively easy association but much more difficult dissociation. In astrophysical regions that are cold and diffuse, such associations could lead to the formation of novel molecules utilizing water (or H2S) as the building blocks of more rich subsequent chemistry. Recent work has hypothesized that oxywater (H2OO) may be an intermediate in the formation of molecular oxygen in comets, and this work supports such a conclusion at least from a molecular cation perspective.