丙醇质谱的abinitio计算  

Ab Initio Calculation on the Mass Spectrum of Propanol

作　　者：毛燕梅[1] 梁宇[2] 钟凯[1] 

机构地区：[1]北方工业大学基础学院,北京石景山100041 [2]北京大学化学与分子工程学院,北京海淀区100871

出　　处：《北方工业大学学报》2000年第3期42-48,共7页Journal of North China University of Technology

基　　金：北方工业大学科研基金

摘　　要：对丙醇质谱实验结果再次进行研究并根据量子化学计算结果进行解释 ,以 MP2 /6-3 1 G* * //UHF/6-3 1 G* * +ZPE基组对丙醇质谱涉及到的离子构型进行分子轨道计算 ,讨论在质谱分析条件下 ,丙醇分子离子及其碎片发生单分子反应 :失氢、重排、异构化、裂分反应 ,指出质谱碎片离子及碎片离子结构 ,解释在质谱图中没有分子离子的原因 .C3 H7O+离子异构化可以形成多种离子 ,包括多种乙烯分子和质子化甲醛离子的配合物 .指出在理论上可以存在 ,而在质谱分析条件下不可能生成的异构体构型 .多个异构反应实质是配位体中 [CH2 OH]+ 和 C2 H4的位置重排 .Quantum chemistry method is used to study the constituted mass spectrum of the propanol. The relative ions and fragments in the mass spectrum of the propanol are re examined. Molecular orbital calculations conducted at the MP2/6 31G ** //UHF/6 31G ** +ZPE level are used to characterize the corresponding potential energy profile. The unimolecular reactions of the molecular ion and the fragments of propanol are investigated, that involve dehydrogenation, rearrangement, isomerization and fragmentation. The resultsof ab initio show the configuration of the fragment ions and the ion neutral complexes and explain why there is no molecuar ion in the mass spectrum. It is explained that some of the theoretical species of ion neutral complexes are unavailable at the mass spectrometry to account for the energies. The ion C 3H 7O + comprises multi isomers consisting of ethene and protoned formaldehyde ions. The isomerization of C 3H 7O + ion is essentially the reorientation of the two partners [CH 2OH] +和C 2H 4.

关 键 词：丙醇 质谱 量子化学 离子-分子化合物 

分 类 号：O623.411[理学—有机化学] O657.63[理学—化学]