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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >State-Specific Reactions of Cu+(S-1,D-3) with SF6 and SF5Cl
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State-Specific Reactions of Cu+(S-1,D-3) with SF6 and SF5Cl

机译：Cu +（S-1，D-3）与SF6和SF5Cl的状态特定反应

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State-specific reactions of Cu+(S-1,D-3) were carried out in a selected ion drift cell apparatus with SF6 and SF5Cl. Copper ions were prepared in a glow discharge utilizing Ne as the working gas. Analysis of Cu+ states using ion mobility mass spectrometry (IMS) indicated the presence of both Ce+(3d(10)) and Cu+(3d(9)4s(1)) configurations attributable to the S-1 ground and D-3 first excited states of this metal ion, respectively. State-specific product formation in reactions of these ions with the two neutral substrates of interest here was determined using IMS along with both known and calculated energetic requirements for product formation. These experiments indicate that Cu+(S-1) associates with both SF6 and SF5Cl; however, the process is approximately four times as efficient with the latter neutral under these conditions. Association is also observed as a minor product between Cu+(D-3) and both neutral reactants. Inefficient formation of SF3+ occurs as the sole bimolecular product from SF6 via Cu+(D-3). In contrast, Cu+(D-3) reacts with SF5Cl in rapid parallel bimolecular processes yielding SF3+ and CuCl. These results also indicate that CuCl initiates additional higher-order processes which result in SF5+ and SF4Cl+. The energetics associated with the formation of SF3+ suggest that a copper halide neutral byproduct must also be formed, requiring a more complex mechanism than simple dissociative charge-transfer.
机译：Cu +（S-1，D-3）的状态特异性反应是在所选的离子漂移池设备中使用SF6和SF5Cl进行的。使用Ne作为工作气体在辉光放电中制备铜离子。使用离子迁移质谱（IMS）分析Cu +态表明存在Ce +（3d（10））和Cu +（3d（9）4s（1））构型，这归因于S-1地和首先激发的D-3金属离子的状态。这些离子与两种目标中性底物的反应中特定于状态的产物形成均使用IMS以及产物形成的已知和计算出的能量需求进行了测定。这些实验表明Cu +（S-1）与SF6和SF5Cl缔合。但是，在这些条件下，采用中性工艺的效率约为后者的四倍。还观察到缔合是Cu +（D-3）与两种中性反应物之间的次要产物。 SF3 +的无效形成是通过SF6通过Cu +（D-3）生成的唯一双分子产物。相反，Cu +（D-3）在快速平行双分子过程中与SF5Cl反应，生成SF3 +和CuCl。这些结果还表明，CuCl引发了其他更高阶的过程，从而导致了SF5 +和SF4Cl +。与SF3 +形成相关的能量学表明，还必须形成卤化铜中性副产物，与简单的解离电荷转移相比，它需要更复杂的机理。

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