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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reaction of Mass-Selected, Thermalized VnOm+ Clusters with CCl4
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Reaction of Mass-Selected, Thermalized VnOm+ Clusters with CCl4

机译：用CCL4的质量选择的热化Vnom +簇的反应

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摘要

The kinetics of VnOm+ + CCl4 (n, m = 2, 5; 3, 6-8; 4, 9-11; 5, 12-13) have been measured under thermal conditions using a selected-ion flow tube equipped with a laser vaporization ion source. All reactions proceed at approximately the capture rate limit, yielding three dominant categories of products: CCl3+ + VnOmCl (i.e., chloride transfer), COCl2 (phosgene) formation, and CO2 formation. Both CO2 and COCl2 are products of CCl4 reaction on a bulk vanadium oxide surface, while chloride (or chlorine) transfer is not observed. The product branching fraction of CCl3+ approaches 100% for small (V-2) reactants and generally decreases with increasing cluster size down to <5% for V5O13. The fraction of chloride transfer is correlated to the fraction of terminal oxygen atoms in the VnOm+ reactant. As cluster size increases, phosgene replaces chloride transfer as the dominant product channel. The channel producing CO2 is observed only for highly oxygenated clusters, V3O8+, V4O11+, and V5O13+, and appears to require a superoxide O-2 in the reactant structure; the mechanism is likely distinct from that producing CO2 on bulk V2O5. Increasing the temperature of the system from 300 to 500 K increases the observed fraction of CCl3+ at the expense of all other product channels. Likely mechanisms, informed by density functional calculations, are discussed.
机译：使用配备有激光的选定离子流管，在热条件下测量Vnom + + Ccl4（n，m = 2,5; 3,6-8; 4,9-11; 5,12-13）的动力学已经在热条件下测量。汽化离子源。所有反应大约进行捕获率限制，产生三种优势类别：CCl3 + + VNOMCL（即氯化物转移），COCl2（光气）形成和CO 2形成。 CO 2和COCl2都是CCl4反应的产物在散装氧化物表面上，而未观察到氯化物（或氯）转移。 CCL3 +的产物分支级分100％用于小（V-2）反应物，并且通常随着簇大小的增加降低至V5O13的<5％。氯化物转移的级分与VNOM +反应物中的末端氧原子的级分相关。随着簇尺寸的增加，光气以取代氯传输作为主要产品通道。仅针对高氧化簇，V3O8 +，V4O11 +和V5O13 +观察到产生CO 2，并且似乎在反应性结构中需要超氧化物O-2;该机制可能与在散装V2O5上产生的CO2不同。将系统的温度从300升至500k增加，增加了所有其他产品通道的CCL3 +的分数。讨论了密度函数计算的可能机制。

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