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OALib Journal期刊
ISSN: 2333-9721
费用：99美元
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杂苯C5H5X(X＝N,P,As,Sb,Bi)芳香性的核独立化学位移(NICS)与异构体稳定化能(ISE)研究
DOI: 10.6023/A12090716, PP. 126-132
Keywords: 杂苯,芳香性,核独立化学位移,异构体稳定化能,自然定域分子轨道
Abstract:
应用量子化学方法,通过核独立化学位移(NICS)和异构体稳定化能(ISE)的计算,研究了苯及第五主族元素取代杂苯分子C5H5X(X＝N,P,As,Sb,Bi)的芳香性与稳定性.局域轨道定位函数局部最大值的计算结果表明,分子中C—X成键强度与实验稳定性顺序一致.从头算与密度泛函理论对分子的化学位移计算结果各异,计算值与实验值相关分析表明,Hartree-Fock方法对所研究体系的NICS比密度泛函理论具有更好的相关性.在分子环平面上方0.8～0.9？处的NICS是芳香性判据的最佳选择,由自然定域分子轨道分解NICS最大处的zz张量值,结果显示π键对分子的芳香性起主要贡献.异构体稳定化能与NICS(max)的zz张量及π键(NICS(max)zzπ)均有很好的相关性,可以表征杂苯分子C5H5X全局芳香性,其顺序为苯＞吡啶＞磷杂苯＞砷杂苯＞锑杂苯＞铋杂苯.特别地,对这类分子π轨道的研究发现不包含X原子的π轨道将产生异常大的π键芳香性,这一现象可为分子磁性设计提供理论指导.
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