Theoretical investigation of the molecular structures and excitation spectra of triphenylamine and its derivatives
Theoretical investigation of the molecular structures and excitation spectra of triphenylamine and its derivatives
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三苯胺及其衍生物的分子结构和激发光谱的理论研究
DOI：
10.1016/j.saa.2011.06.069
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
H.Fujimoto
中科院分区：
文献类型：
--
作者：
M.Sumimoto;D.Yokogawa;M.Komeda;H.Yamamoto;K.Hori;H.Fujimoto
采用密度泛函理论和post-Hartree-Fock方法研究了NPh 3、NPh 2 Me、NPhMe 2和NMe 3的分子几何构型、电子结构和激发能。当这些化合物的结构稳定性进行比较，通过使用MP4（SDQ）方法获得的结果，它被证实，通过使用MP2方法优化的几何结构是足够可靠的。具有大振子强度的激发态由HOMO的跃迁分量组成。应该注意的是，在HOMO中，氮原子的轨道与苯基的π轨道以反键方式混合，并且轨道能量随着这种混合而增加。未占据轨道是由苯基的π轨道之间的成键和反键型相互作用产生的;因此，苯基的数量强烈影响所研究的化合物的能量图。能量图中的差异导致这些化合物在紫外区的光谱变化。
The molecular geometries, electronic structures, and excitation energies of NPh3, NPh2Me, NPhMe2, and NMe3, were investigated using DFT and post-Hartree Fock methods. When the structural stabilities of these compounds were compared to results obtained by using MP4(SDQ) method, it was confirmed that the optimized geometries by using MP2 method were sufficiently reliable. The excited states with large oscillator strengths consisted of transition components from the HOMO. It should be noted that the orbitals of the nitrogen atom mix with the π-orbital of the phenyl group in an anti-bonding way in the HOMO, and the orbital energy increases with this mixing. The unoccupied orbitals are generated from bonding and anti-bonding type interactions between the π-orbitals of the phenyl groups; therefore, the number of phenyl groups strongly affects the energy diagram of the compounds studied. The differences in the energy diagram cause a spectral change in these compounds in the ultraviolet region.