Chemical Pathways of SO2 with Hydrogen Atoms on Interstellar Ice Analogues

Thanh Nguyen, Yasuhiro Oba, W. M. C. Sameera, Kenji Furuya and Naoki Watanabe
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Abstract

Sulfur dioxide (SO2) is a sulfur-containing molecule expected to exist as a solid in the interstellar medium. In this study, we have performed laboratory experiments and computational studies on the surface reactions of solid SO2 with hydrogen atoms on amorphous solid water (ASW) at low temperatures. After 40 minutes of exposure of SO2 deposited on ASW to H atoms, approximately 80% of the solid SO2 was lost from the substrate at 10–40 K, and approximately 50% even at 60 K, without any definite detection of reaction products. Quantum chemical calculations suggest that H atoms preferentially add to the S atom of solid SO2, forming the HSO2 radical. Further reactions of the HSO2 radical with H atoms result in the formation of several S-bearing species, including HS(O)OH, the S(O)OH radical, HO–S–OH, HS–OH, and H2S. In codeposition experiments involving H and SO2, we have confirmed the formation of H2S, HS(O)OH, and/or HO–S–OH. However, the yields of these S-bearing species are insufficient to account for the complete loss of the initial SO2 reactant. These findings suggest that some products are desorbed into the gas phase upon formation. This study indicates that a portion of the SO2 in ice mantles may remain unreacted, avoiding hydrogenation, while the remainder is converted into other species, some of which may be subject to chemical desorption.
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星际冰模拟物上二氧化硫与氢原子的化学路径
二氧化硫(SO2)是一种含硫分子,预计会以固体形式存在于星际介质中。在这项研究中,我们对无定形固体水(ASW)上的固体二氧化硫在低温下与氢原子的表面反应进行了实验室实验和计算研究。将沉积在 ASW 上的 SO2 与氢原子接触 40 分钟后,在 10-40 K 的温度下,约有 80% 的固体 SO2 从基底上流失,在 60 K 的温度下甚至有约 50% 的固体 SO2 从基底上流失,但没有检测到任何明确的反应产物。量子化学计算表明,H 原子优先加到固体 SO2 的 S 原子上,形成 HSO2 自由基。HSO2 自由基与 H 原子的进一步反应会形成多种含 S 的物质,包括 HS(O)OH、S(O)OH 自由基、HO-S-OH、HS-OH 和 H2S。在涉及 H 和 SO2 的共沉积实验中,我们证实了 H2S、HS(O)OH 和/或 HO-S-OH 的形成。然而,这些含 S 物种的产量不足以解释初始 SO2 反应物的完全损失。这些发现表明,一些产物在形成后会解吸进入气相。这项研究表明,冰幔中的一部分二氧化硫可能仍未发生反应,从而避免了氢化,而剩余的二氧化硫则转化成了其他物种,其中一些物种可能会发生化学解吸作用。
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