UV-to-IR Absorption of Molecularly p-Doped Polythiophenes with Alkyl and Oligoether Side Chains: Experiment and Interpretation Based on Density Functional Theory.
UV-to-IR Absorption of Molecularly p-Doped Polythiophenes with Alkyl and Oligoether Side Chains: Experiment and Interpretation Based on Density Functional Theory.
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含烷基和低聚醚侧链的分子p型掺杂聚噻吩的紫外到红外吸收：基于密度泛函理论的实验与解析
DOI：
10.1021/acs.jpcb.0c08757
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发表时间：
2020-12-10
期刊：
影响因子：
--
通讯作者：
Zozoulenko I
中科院分区：
文献类型：
--
作者：
Sahalianov I;Hynynen J;Barlow S;Marder SR;Müller C;Zozoulenko I
利用吸收光谱和密度泛函理论(DFT)计算方法，研究了含烷基侧链的P掺杂聚3-己基噻吩基(P3HT)和含四甘醇侧链的极性聚噻吩环(P3HT)的UV-IR跃迁。电子结构随掺杂水平的变化而变化，同时考虑了掺杂离子、链扭曲和π-π堆积的作用，这些作用中的每一个都具有加宽吸收峰而不显著改变其位置的效果。计算得到的光谱与二硫杂钼配合物掺杂聚合物的实验光谱符合得很好。就像在其他掺杂共轭聚合物的密度泛函研究中一样，出现的电子结构和光学跃迁的分配与早期的“传统”方法得到的结果有本质的不同。特别是，对于P掺杂材料，极化子和双极化子/极化子对都存在两个显著的带。这些跃迁的最低能量是由于从价带到位于带隙中的自旋分辨轨道的激发。高能带是价带到能隙中自旋分辨轨道的激发和带间激发的叠加。
The UV-to-IR transitions in p-doped poly(3-hexylthiophene) (P3HT) with alkyl side chains and polar polythiophene with tetraethylene glycol side chains are studied experimentally by means of the absorption spectroscopy and computationally using density functional theory (DFT) and tight-binding DFT. The evolution of electronic structure is calculated as the doping level is varied, while the roles of dopant ions, chain twisting, and π–π stacking are also considered, each of these having the effect of broadening the absorption peaks while not significantly changing their positions. The calculated spectra are found to be in good agreement with experimental spectra obtained for the polymers doped with a molybdenum dithiolene complex. As in other DFT studies of doped conjugated polymers, the electronic structure and assignment of optical transitions that emerge are qualitatively different from those obtained through earlier “traditional” approaches. In particular, the two prominent bands seen for the p-doped materials are present for both polarons and bipolarons/polaron pairs. The lowest energy of these transitions is due to excitation from the valence band to a spin-resolved orbitals located in the gap between the bands. The higher-energy band is a superposition of excitation from the valence band to a spin-resolved orbitals in the gap and an excitation between bands.
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影响因子：
15
作者：
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通讯作者：
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影响因子：
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