Rebbert R E, Ausloos P
Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234.
J Res Natl Bur Stand A Phys Chem. 1972 Jul-Aug;76A(4):329-336. doi: 10.6028/jres.076A.032.
The pulse radiolysis of gaseous neopentane has been investigated in the absence and presence of electron scavengers (SF, CDI, CCl). Deuterium labeling experiments show that the stable product molecules can be accounted for by (a) radical combination reactions involving mainly CH and H; (b) hydride ion transfer reactions involving CH , CH , and CH ; (c) neutralization reactions of CH and CH ; and (d) unimolecular dissociation of the parent ion (CH ) and of electronically excited neopentane. Neutralization of the -CH ion, which is the major positive ion in the system occurs as follows: (a) -CH + e → -CH + H and (b) -CH + → 2CH + CH. It is shown that CH produced in hydride ion transfer reaction C H + neo-CH → C H + CH (where C H = CH , CH , and CH ) rearranges to the CHC(CH)CHCH structure prior to neutralization. A detailed accounting of all products produced in the unimolecular and bimolecular reactions led to the conclusion that the ratio of neutral electronically excited molecules to parent ions (N/N) is 0.28.
在不存在和存在电子清除剂（SF、CDI、CCl）的情况下，对气态新戊烷的脉冲辐解进行了研究。氘标记实验表明，稳定产物分子可通过以下方式解释：（a）主要涉及CH和H的自由基组合反应；（b）涉及CH 、CH 和CH 的氢负离子转移反应；（c）CH 和CH 的中和反应；以及（d）母离子（CH ）和电子激发新戊烷的单分子解离。系统中的主要正离子-CH 的中和反应如下：（a）-CH + e → -CH + H 和（b）-CH + → 2CH + CH。结果表明，在氢负离子转移反应C H + neo-CH → C H + CH （其中C H = CH 、CH 和CH ）中产生的CH 在中和之前重排为CHC(CH)CHCH结构。对单分子和双分子反应中产生的所有产物进行详细核算后得出结论，中性电子激发分子与母离子的比例（N/N）为0.28。
