摘要
用密度泛函方法BHandHlYP以6 311+G(d)和6 311+G(2df)为基组对草酰溴的一价正离子(BrCO)+2和中性分子(BrCO)2做了构象分析,结果表明,(BrCO)+ 2和(BrCO)2都具有平面反式和交叉式两种构象。交叉式构象存在超共轭现象。此外,对草酰溴离子、中性分子各解离通道初级反应的Gibbs自由能的计算,发现草酰溴离子C C键解离通道的反应活性总体上大于中性分子,对该反应通道进一步做了反应机理研究,证实了热力学结论。
The conformers of oxalyl bromide cation (BrCO)^+_2 is studied by using BHandHLYP level of theory at 6-331+G(d)and 6-311+G(2df)basis sets.It is found that (BrCO)^+_2 has trans and gauche conformers and hyperconjugation effect make the gauche form to stabilized.The study of the dissociation reaction Gibbs free energy of oxalyl bromide cation (BrCO)^+_2 and neutral molecule (BrCO)_2 show that the dissociation of C-C bond in (BrCO)^+_2 is easier than that in (BrCO)_2.
出处
《化学研究与应用》
CAS
CSCD
北大核心
2005年第1期42-45,共4页
Chemical Research and Application
基金
甘肃省教育厅科研基金资助课题
