Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
J Phys Chem A. 2010 Dec 30;114(51):13296-302. doi: 10.1021/jp107913p. Epub 2010 Dec 3.
Direct current (DC) slice imaging of state-selected ions is combined with high-level ab initio calculations to give insight into reaction pathways, dynamics, and energetics for ethylamine cation photodissociation at 233 nm. These reaction pathways are of interest for understanding the rich chemistry of Titan's ionosphere recently revealed by the Cassini mission. The result for the H-loss product has a bimodal translational energy distribution, indicating two distinct H-loss pathways: these are assigned to triplet CH(3)CH(2)NH(+) product ions and the singlet CH(3)CHNH(2)(+) species. The distribution shows a modest fraction of energy available in translation and is consistent with barrierless dissociation from the ground state. HCNH(+) formation is observed as the dominant channel and exhibits a bimodal translational energy distribution with the faster component depicting a significant angular anisotropy. This suggests a direct excited-state decay pathway for this portion of the distribution. We have also observed the H + H(2) loss product as a minor secondary dissociation channel, which correlates well with the formation of CH(2)CNH(2)(+) ion with an exit barrier.
直流(DC)切片成像与高级从头算相结合,深入了解乙基胺阳离子在 233nm 处光解的反应途径、动力学和能量学。这些反应途径对于理解卡西尼任务最近揭示的泰坦电离层丰富的化学性质很有意义。对于 H 损失产物,结果具有双峰平移能分布,表明存在两种不同的 H 损失途径:这些途径被分配给三重态 CH(3)CH(2)NH(+)产物离子和单重态 CH(3)CHNH(2)(+)物种。该分布显示出可用于平移的能量的适度分数,并且与从基态无势解离一致。HCNH(+)的形成被观察为主要通道,并表现出双峰平移能分布,较快的分量描绘出显著的角各向异性。这表明该分布的这一部分存在直接的激发态衰减途径。我们还观察到 H + H(2)损失产物作为次要的二级解离通道,这与 CH(2)CNH(2)(+)离子的形成很好地相关,该离子具有出口势垒。