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The kinetic energy dependence of association reactions.A new thermokinetic method for large systems

机译:缔合反应的动能依赖性。一种用于大型系统的新热动力学方法

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The reactions of bare alkali metal ions (M~+=Li~+,Na~+,or K~+)with dimethoxyethane (CH_3OCH_2CH_2OCH_3,DEX)are studied using guided ion beam tandem mass apectrometry.The bimolecular reaction forms an associative M~+(DXE)complex that is long-lived and dissociates back to the reactants.The kinetic energy dependences of the cross sections for formation of the complexes are interpreted wtih several different models (including rigorous phase space theory)that assume that the complex lifetimes are limited by dissociation over a losse,orbiting transition state.After accounting for the effects of multiple ion-molecule collisions,internal energy of the reactant ions.Doppler broadening,and dissociatio lifetimes,the analyses yield 0 K bond energies as the only adjustable parameter.These values are compared wtih bond energies obtained from previous collision-induced dissociation (CID)studies of the M~+(DEX)complexes and found to be self-consistent for all models studied.Association and CID form the same energized M~+(DXE) complex in two distinct ways,such that a comparison of these results allows an assessement of teh models used to interpret CID thresholds and test the limits of statistical theories such as RRKM and phase space theory.
机译:用导向离子束串联质谱法研究了裸碱金属离子(M〜+ = Li〜+,Na〜+或K〜+)与二甲氧基乙烷(CH_3OCH_2CH_2OCH_3,DEX)的反应,双分子反应形成缔合的M〜 +(DXE)络合物长寿命并离解回反应物。通过几种不同的模型(包括严格的相空间理论)解释了络合物形成的横​​截面的动能依赖性,这些模型假定络合物的寿命为在考虑了多个离子-分子碰撞,反应离子的内部能量,多普勒展宽和离解寿命的影响后,分析得出0 K键能是唯一可调整的参数。将这些值与从以前的M〜+(DEX)络合物的碰撞诱导解离(CID)研究获得的键能进行比较,发现在所有研究的模型中它们都是自洽的。相同的激发M〜+(DXE)络合物可以通过两种不同的方式进行比较,因此,通过比较这些结果,可以评估用于解释CID阈值的模型,并测试RRKM和相空间理论等统计理论的极限。

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