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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactions of Cu+(S-1, D-3) with CH3Cl, CH2ClF, CHCIF2, and CClF3
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Reactions of Cu+(S-1, D-3) with CH3Cl, CH2ClF, CHCIF2, and CClF3

机译：Cu +（S-1，D-3）与CH3Cl，CH2ClF，CHClF2和CClF3的反应

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摘要

The reactions of gas-phase Cu+(S-1) and Cu+(D-3) with CH3CL, CH2ClF, CHClF2, and CCIF3 are examined using the drift cell technique at 3.5 Torr. State-specific product channels and overall bimolecular rate constants for depletion of the two Cu+ states are determined using, electronic state chromatography. Cu+(S-1) participates exclusively in association with all four neutrals, whereas Cl abstraction is the dominant product channel for CU+(D-3). The resulting CuCl+ product subsequently abstracts Cl- in a secondary process. Tertiary reactions are also observed, which include both hydride abstraction (with CH3Cl) and fluoride abstraction (with the fluorinated neutrals). All product channels can be understood in terms of the known thermochemical and quantum mechanical (i.e., spin) requirements. Cu+(S-1) is depleted by all four neutrals at 30% to 40% of the ADO rate under these conditions, whereas Cu+(3D) is observed to react at approximately 80% of the ADO rate with CH3Cl, CH2ClF, and CHClF2. Reaction of excited state Cu+ with CClF3 occurs at only 7% of the ADO rate. The behavior Of CU+(D-3) is consistent with a mechanism in which formation of CuCl+ occurs exclusively on the triplet surface via a mechanism in which the metal ion must interact exclusively with Cl.
机译：使用漂移池技术在3.5 Torr下检查了气相Cu +（S-1）和Cu +（D-3）与CH3CL，CH2ClF，CHClF2和CCIF3的反应。使用电子状态色谱法确定两个Cu +态耗竭的特定于状态的产物通道和总体双分子速率常数。 Cu +（S-1）仅与所有四个中性有关，而Cl抽象是CU +（D-3）的主要产物通道。生成的CuCl +产物随后在次级过程中提取Cl-。还观察到了三次反应，包括氢化物抽象（用CH3Cl）和氟化物抽象（用氟化的中性物）。可以根据已知的热化学和量子力学（即旋转）要求来理解所有产品通道。在这些条件下，所有四个中性物质都以ADO速率的30％至40％耗尽了Cu +（S-1），而观察到Cu +（3D）以ADO速率的约80％与CH3Cl，CH2ClF和CHClF2反应。激发态Cu +与CClF3的反应仅发生ADO速率的7％。 CU +（D-3）的行为与通过金属离子必须仅与Cl相互作用的机理而仅在三重态表面上形成CuCl +的机理一致。

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