Reactions of hydrogen atoms with small sulfur-containing anions, SCN^–, CH₃COS^–, C₆H₅COS^–, ^–SCH₂COOH, C₆H₅S^–, 2-HOOCC₆H₄S^–, and related oxygen-containing anions, OCN^–, CH₃COO^–, C₆H₅COO^–, HOCH₂COO^–, C₆H₅O^–, 2-HOOCC₆H₄O^–, have been studied both experimentally and computationally. The experimental results show that associative electron detachment (AED) is the only channel for the reactions. The rate constants for reactions between sulfur-containing anions and H atoms are generally higher than for the related oxygen-containing anions with the exception of the reaction of SCN^–. The generally higher reactivity of the sulfur anions contrasts with previous results where AED reactivity was found to correlate with reaction exothermicity. Density functional theory calculations indicate that the reaction enthalpies, the characteristics of the reaction potential energy surfaces, and other structural and electronic factors can influence the reaction rate constants. This study indicates that organic sulfur anions can be more reactive than related oxygen anions in the interstellar medium where hydrogen atoms are abundant.

中文翻译：

---

含硫和氧的阴离子与氢原子的反应：比较研究

氢原子与小的含硫阴离子SCN ^–，CH ₃ COS ^–，C ₆ H ₅ COS ^–，^– SCH ₂ COOH，C ₆ H ₅ S ^–，2-HOOCC ₆ H ₄ S ^–以及相关氧的反应含阴离子，OCN ^–，CH ₃ COO ^–，C ₆ H ₅ COO ^–，HOCH ₂ COO ^–，C ₆ H ₅ O ^–，2-HOOCC ₆ H ₄ O ^–，已经在实验和计算上进行了研究。实验结果表明，缔合电子脱离（AED）是反应的唯一通道。除SCN的反应外，含硫阴离子与H原子之间反应的速率常数通常高于相关的含氧阴离子^。。硫阴离子的反应性通常较高，与先前的结果相反，先前的结果发现AED反应性与反应放热相关。密度泛函理论计算表明，反应焓，反应势能面的特征以及其他结构和电子因素均可影响反应速率常数。这项研究表明，在氢原子丰富的星际介质中，有机硫阴离子比相关的氧阴离子更具反应性。