Liu Shu, Zhang Dong H
State Key Laboratory of Molecular Reaction Dynamics , Dalian Institute of Chemical Physics , Chinese Academy of Sciences , Dalian 116023 , Liaoning , China . Email:
Chem Sci. 2016 Jan 1;7(1):261-265. doi: 10.1039/c5sc03472h. Epub 2015 Sep 29.
A local mode picture was postulated some time ago to explain the negligible OD product excitation from H reacting with DO in fundamental asymmetrical excitation: the DO asymmetric stretch state is best thought as a linear combination of local mode stretches with the H atom reacting preferentially with the excited OD bond, but has never been verified. Here we report the first full-dimensional state-to-state study for the title reaction with HO in the ground and the first symmetric and asymmetric stretching excited states. It is found that symmetric and asymmetric stretching excited states, which vibrate in very different ways in the normal mode picture, behave essentially identically in the reaction. More importantly, our calculations revealed that the reaction produces a small fraction of OH in the = 1 state, with the population close to the relative reactivity between the ground and vibrationally excited states, and therefore it confirms the local mode picture for HO in symmetric or asymmetric stretch states when reacting with an H atom.
不久前有人提出一种局域模式图景，以解释在基频非对称激发下，氢与重水反应产生的可忽略不计的OD产物激发情况：DO非对称伸缩态最好被视为局域模式伸缩的线性组合，其中氢原子优先与激发的OD键反应，但这从未得到验证。在此，我们报告了首个针对该标题反应在基态以及首个对称和非对称伸缩激发态下与HO进行的全维态-态研究。研究发现，在简正模式图景中以非常不同方式振动的对称和非对称伸缩激发态，在反应中表现基本相同。更重要的是，我们的计算表明，该反应产生一小部分处于(v = 1)态的OH，其布居数接近基态与振动激发态之间的相对反应活性，因此证实了HO在与氢原子反应时处于对称或非对称伸缩态的局域模式图景。
