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含能材料  2003 

叠氮甲烷二聚体分子间相互作用的abinitio研究

Keywords: 物理化学,叠氮甲烷二聚体,分子间相互作用,从头计算,自然键轨道分析,IR光谱,热力学性质

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Abstract:

运用abinitio方法,在HF水平6-311G**基组下求得叠氮甲烷二聚体势能面上六种优化构型和电子结构。经MP2电子相关和基组叠加误差(BSSE)以及零点能(ZPE)校正,求得分子间相互作用能;结合能(9.49kJ·mol-1)最大的二聚体为存在两个C-H...N氢键的六元环构型,属于D2h群。探讨了甲基内旋转对相互作用能的影响。由自然键轨道(NBO)分析揭示了相互作用的本质。对单体和六种二聚体优化构型进行简谐振动分析,研究了IR光谱变化规律。此外还基于统计热力学求得273.15~800.00K温度范围从单体形成二聚体的热力学性质变化。

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