Ab Initio Classical Trajectory Study of the Dissociation of Neutral and Positively Charged Methanimine (CH2NHn n=0-2)

作者：Zhou Jia; Schlegel H Bernhard^*

来源：Journal of Physical Chemistry A, 2009, 113(37): 9958-9964.

DOI：10.1021/jp905420v

The structures and energetics of the reactants, intermediates, transition states, and products for the dissociation of methanimine neutral, monocation, dication, and trication were calculated at the CBS-APNO level of theory. The dissociations of the neutral, monocation, and dication were studied by ab initio direct classical trajectory calculations at the B3LYP/6-311 G(d,p) level of theory. A microcanonical ensemble Using quasiclassical normal mode sampling was constructed by distributing 200, 150, and 120 kcal/mol of excess energy above the local minima of the neutral, singly, and doubly charged species, respectively. Many of the trajectories dissociate directly to produce H+, H atom. or H-2. However, for a fraction of the cases, substantial migration of the hydrogen occurs within the molecule before dissociation. The preferred dissociation product for the neutral and the monocation is hydrogen atom. Elimination of H-2 was seen in 20% of the trajectories for the neutral and in 5% of the trajectories for the monocation. Dissociations of the dication and trication produced H+ rather than H atom. HCNH+ was formed in 85-90% of the dissociating trajectories for the monocation and dication.

• 出版日期2009-9-17