溴代类卡宾H2CMBr(M=Na,K)的结构与稳定性

本文用RHF/3-21G^*解析梯度方法研究了溴代类卡宾H2CMBr(M=Na,K)势能面的主要特征, 得到了它们各自的三种平衡构型及两种异构化的过渡态构型, 并用二级微扰方法进行了能量的相关能校正, 计算了振动频率, 以确证平衡构型和过渡态。计算结果表明, 溴代类卡宾H2CMBr(M=N,K))的三元环构型是最稳定的几何构型, 其它的两种构型σ-配合物和p-配合物, 也是势能面上的极值点, 但能量相对较高, 不稳定。本文分析了各构型的特点, 对其化学反应特性进行了评估。

Structures and stabilities of brocarbenoids H2CMBr(M=Na,K)

Main characters of the potential energy surface of brocarbenoids H2CMBr(M=Na,K) have been studied by RHF/3-21G^* gradient method. Three equilibrium structures and two isomerization transition states are located. The electron correlation energies have been calculated at the second-order (MP2) perturbation theory and harmonic vibrational frequencies have also been executed. Energies of the equilibrium states are in the order of 1 (three-membered ring form)<3(p-complex)<2(σ-complex). 1 is predicted to be the form in which H2C MBr exists and takes part in reactions. The Mulliken populations and zero-point energies are also given.