Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
J Chem Phys. 2013 Nov 14;139(18):181103. doi: 10.1063/1.4830397.
The ejection of triatomic hydrogen molecular ions HD2(+) and D3(+) from CD3OH(2+) is investigated by first-principle molecular dynamics simulation. Two C-D chemical bonds are found to be broken to form a neutral D2 moiety that vibrates, rotates, and moves for a relatively long period of time (20-330 fs) towards a transition state leading to the ejection of HD2(+) or D3(+). The formation of such a long-lived neutral D2 moiety within a hydrocarbon molecule interprets well the recent experimental findings of the long lifetime of doubly charged energized hydrocarbon molecules prior to the ejection of H3(+).
通过第一性原理分子动力学模拟研究了 CD3OH(2+) 中三原子氢分子离子 HD2(+) 和 D3(+) 的喷射。发现两个 C-D 化学键断裂，形成一个中性 D2 部分，该部分振动、旋转并相对较长时间（20-330fs）向过渡态移动，导致 HD2(+) 或 D3(+) 的喷射。在烃分子中形成这种长寿命的中性 D2 部分很好地解释了最近实验发现的，在 H3(+) 喷射之前，双重电荷激发的烃分子具有长寿命。
