Proposed Importance of HOCO Chemistry: Inefficient Formation of CO2 from CO and OH Reactions on Ice Dust

Atsuki Ishibashi, Germán Molpeceres, Hiroshi Hidaka, Yasuhiro Oba, Thanja Lamberts and Naoki Watanabe
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Abstract

With the advent of JWST ice observations, dedicated studies on the formation reactions of detected molecules are becoming increasingly important. One of the most interesting molecules in interstellar ice is CO2. Despite its simplicity, the main formation reaction considered, CO + OH → CO2 + H through the energetic HOCO* intermediate on ice dust, is subject to uncertainty because it directly competes with the stabilization of HOCO as a final product, which is formed through energy dissipation of HOCO* to the water ice. When energy dissipation to the surface is effective during the reaction, HOCO can be a dominant product. In this study, we experimentally demonstrate that the major product of the reaction is indeed not CO2, but rather the highly reactive radical HOCO. The HOCO radical can later evolve into CO2 through H-abstraction reactions, but these reactions compete with additional reactions, leading to the formation of carboxylic acids (R-COOH). Our results highlight the importance of HOCO chemistry and encourage further exploration of the chemistry of this radical.
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HOCO 化学的拟议重要性:冰尘上 CO 和 OH 反应生成 CO2 的效率低下
随着 JWST 冰观测的出现,对探测到的分子的形成反应进行专门研究正变得越来越重要。星际冰中最有趣的分子之一是 CO2。所考虑的主要形成反应(CO + OH → CO2 + H,通过冰尘上的高能 HOCO* 中间体)尽管简单,但却存在不确定性,因为它直接与作为最终产物的 HOCO 的稳定化相竞争,而 HOCO 的稳定化是通过 HOCO* 对水冰的能量耗散形成的。当反应过程中向表面的能量耗散有效时,HOCO 会成为主要产物。在本研究中,我们通过实验证明,反应的主要产物确实不是二氧化碳,而是高活性自由基 HOCO。HOCO 自由基随后可通过 H-萃取反应演变成 CO2,但这些反应会与其他反应发生竞争,从而形成羧酸(R-COOH)。我们的研究结果突显了 HOCO 化学的重要性,并鼓励进一步探索这种自由基的化学性质。
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