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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Generation of Neutral CCCCBO in the Gas Phase from [CCCCBO]~- and Rearrangement of Energized CCCCBO to OCCCCB: A Joint Experimental and Theoretical Investigation
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Generation of Neutral CCCCBO in the Gas Phase from [CCCCBO]~- and Rearrangement of Energized CCCCBO to OCCCCB: A Joint Experimental and Theoretical Investigation

机译：[CCCCBO]〜-气相中性CCCCBO的产生以及加能CCCCBO重排为OCCCCB：联合实验和理论研究

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摘要

One-electron vertical Franck-Condon oxidation of [CCCCBO]~- (using O_2 as collision gas in the dual collision cell region of an HF-ZAB/AMD 604 four-sector mass spectrometer) forms doublet neutrals C_4BO in the first stage of a neutralization-reionization (~-NR~+) experiment. Reionization of these neutrals to decomposing positive ions shows that the majority of neutrals (formed in the first collision cell) correspond to CCCCBO which are stable for the microsecond duration of the NR experiment. However, a minor fraction of neutrals CCCCBO is energized and rearranges to form an isomer which decomposes by loss of CO. A theoretical study of this system at the MP4SDTQ/aug-cc-pVDZ//MP2(full)/6-31G(d) level of theory suggests that the rearranged species corresponds to OCCCCB. The rearrangement occurs by six-center cyclization of CCCCBO, involving O-C(1) bond formation followed by B-O bond cleavage to form OCCCCB. The reaction is endothermic by only 4.5 kcal mol~(-1) but requires an excess energy of ≥ 53.5 kcal mol~(-1) in order for the system to surmount the first transition state. This energy requirement is 45.5 kcal mol~(-1) more than the Franck-Condon excess energy of 8 kcal mol~(-1) of CCCCBO produced by the vertical oxidation process. The additional energy may be provided by keV collisions of CCCCBO with the collision gas O2 following Franck-Condon-controlled neutralization of [CCCCBO]~-.
机译：[CCCCBO]〜-的单电子垂直Franck-Condon氧化（使用O_2作为HF-ZAB / AMD 604四扇区质谱仪的双碰撞池区域中的碰撞气体）在第一阶段形成双重态中性体C_4BO。中和-去离子（〜-NR〜+）实验。这些中性离子的电离分解为正离子表明，大多数中性离子（在第一个碰撞池中形成）对应于CCCCBO，它们在NR实验的微秒内保持稳定。但是，一小部分中性化合物CCCCBO通电并重排形成异构体，该异构体会因CO的损失而分解。在MP4SDTQ / aug-cc-pVDZ // MP2（full）/ 6-31G（d理论水平）表明，重新排列的物种对应于OCCCCB。重排通过CCCCBO的六中心环化发生，涉及O-C（1）键形成，然后B-O键裂解形成OCCCCB。该反应仅吸热4.5 kcal mol〜（-1），但需要过量的能量≥53.5 kcal mol〜（-1）才能使系统克服第一过渡态。该能量需求比通过垂直氧化过程产生的CCCCBO的8kcal mol〜（-1）的弗兰克-康登过量能量多45.5kcal mol〜（-1）。在弗兰克-康登控制的[CCCCBO]〜-中和之后，CCCCBO与碰撞气体O2的keV碰撞可以提供额外的能量。

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