Trapped Abstraction in the O(1D) + CHD3 鈫?OH + CD3 Reaction

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• 作者：Jiayue Yang ; Kejie Shao ; Dong Zhang ; Quan Shuai ; Bina Fu ; Dong H. Zhang ; Xueming Yang
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2014
• 出版时间：September 18, 2014
• 年：2014
• 卷：5
• 期：18
• 页码：3106-3111
• 全文大小：342K
• ISSN：1948-7185

文摘

Despite significant progress made in past decades, it is still challenging to elucidate dynamics mechanisms for polyatomic reactions, in particular, involving complex formation. The reaction of O(¹D) with methane has long been regarded as a prototypical polyatomic system of direct insertion reaction in which the O(¹D) atom can insert into the C鈥揌 bond of methane to form a 鈥渉ot鈥?methanol intermediate before decomposition. Here, we report a combined theoretical and experimental study on the O(¹D) + CHD₃ reaction, on which good agreement between theory and experiment is achieved. Our study revealed that this complex-forming reaction actually proceeds via a trapped abstraction mechanism, rather than an insertion mechanism as has long been thought. We anticipate that this reaction mechanism should also be responsible for the reaction of O(¹D) with ethane and propane, as well as many other chemical reactions with deep wells in the interaction region.

Keywords:

polyatomic reactions; complex-forming; trapped abstraction; crossed molecular beam ion imaging; global PES; QCT