Binding of the atomic cations hydrogen through argon to water and hydrogen sulfide†,Physical Chemistry Chemical Physics

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Binding of the atomic cations hydrogen through argon to water and hydrogen sulfide†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-10-02 00:00:00 , DOI: 10.1039/c8cp05378b
Brent R. Westbrook _{1,

2,

3,

4} , Katelyn M. Dreux _{4,

5,

6} , Gregory S. Tschumper _{4,

5,

6} , Joseph S. Francisco _{4,

7,

8} , Ryan C. Fortenberry _{4,

5,

6}

Affiliation

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.

中文翻译：

氢通过氩气将原子阳离子与水和硫化氢结合†

水和硫化氢将与元素周期表前三行中的每个原子阳离子结合。尽管某些原子比其他原子更紧密地结合，但是显式相关的耦合簇理论计算表明，即使对于稀有气体原子，也需要将能量放入系统中才能解离这些键。最有前途的系统具有浅的入口势能面（PES），位于不同自旋的深井上方。对于H ₂ OO ⁺，H ₂ SS ⁺和H ₂ OS ⁺明确显示了这些孔。重原子键长的松弛PES表示四重态将穿过更深键合的双重态，从而使缔合相对容易，但解离则困难得多。在寒冷和弥漫的天体区域，这种联系可能导致利用水（或H ₂ S）作为更丰富的后续化学反应的基础而形成新分子。最近的工作假设，氧水（H ₂ OO）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。

更新日期：2018-10-02

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