CAJ | 학술논문

采用密度泛函理论(density functional theory DFT)中的杂化密度泛函B3LYP方法,在6-311++G~(**)基组水平上对几种取代苯硫酚分子的构型进行了几何优化,得出了它们的最稳定构型并对其能级差、核独立化学位移、极化率和振动光谱进行了理论计算.研究结果表明,4-巯基吡啶(4-MPY)、4-巯基苯甲酸(4-MBA)和4-巯基苯胺(PATP)均为平面构型,1,4对巯基苯(BDT)中S-H键与苯环平面的夹角为20.2°,4-甲基巯基苯(4-MBT)中S-H键与苯环平面的夹角为39.6°.几种分子都具有很强的芳香性和较大的极化率值.5种分子的极化率张量平均值大小顺序为BDT＞4-MBT＞4-MBA＞4-MPY＞PATP,极化率的各向异性不变量变化趋势为4-MBA＞4-MBT＞BDT＞PATP＞4-MPY.
채용밀도범함이론(density functional theory DFT)중적잡화밀도범함B3LYP방법,재6-311++G~(**)기조수평상대궤충취대분류분분자적구형진행료궤하우화,득출료타문적최은정구형병대기능급차、핵독립화학위이、겁화솔화진동광보진행료이론계산.연구결과표명,4-구기필정(4-MPY)、4-구기분갑산(4-MBA)화4-구기분알(PATP)균위평면구형,1,4대구기분(BDT)중S-H건여분배평면적협각위20.2°,4-갑기구기분(4-MBT)중S-H건여분배평면적협각위39.6°.궤충분자도구유흔강적방향성화교대적겁화솔치.5충분자적겁화솔장량평균치대소순서위BDT＞4-MBT＞4-MBA＞4-MPY＞PATP,겁화솔적각향이성불변량변화추세위4-MBA＞4-MBT＞BDT＞PATP＞4-MPY.
The geometrical structures of several Raman probe molecules were optimized using density functional theory(DFT)of the hybrid density functional B3LYP method and 6-311++G~(**) basis set.Their energy gap,nucleus independent chemical shift (NICS),polarizability and vibration spectrum were studied.The theoretical results showed that:4-MPY,MBA and PATP had planar structures,the angle of BDT between S-H and benzene ring plane was 20.2°,and the 4-MBT was 39.6°;they all have a strong aroma and a large value of polarization.The order of the average of molecular hyperpolarizability tensor was BDT＞4-MBT＞4-MBA＞4-MPY＞PATP,and the trends of polarizability anisotropy invariant were 4-MBA＞4-MBT＞BDT＞PATP＞4-MPY.