Departament d'Enginyeria Química, ETSEIB, Universitat Politècnica de Catalunya, Avda. Diagonal 647, Barcelona E-08028, Spain.
J Phys Chem B. 2010 Mar 18;114(10):3494-9. doi: 10.1021/jp9112574.
The structural and electronic properties of poly(3,4-phenylenedioxythiophene) and poly(3,4-ethylenedioxythiophene) have been studied using quantum mechanical methods. Calculations have been performed considering a series of oligomers up to 12 repeating units in the neutral and cation states, results being used to extrapolate the properties of the two polymers in the undoped and doped states. Moreover, the electronic properties were estimated in the gas phase and acetonitrile solution, the latter solvent being used in the electrogeneration of the two conducting polymers. A detailed analysis of the results indicates that, although the pi-pi* transition energy of poly(3,4-ethylenedioxythiophene) is lower than that of poly(3,4-phenylenedioxythiophene) in the neutral state, the latter behaves as excellent electronic conductor upon p-doping. Accordingly, the oxidized poly(3,4-phenylenedioxythiophene) shows the lowest pi-pi* electron transition energy.
使用量子力学方法研究了聚（3,4-亚苯基二氧噻吩）和聚（3,4-亚乙基二氧噻吩）的结构和电子性质。在中性和阳离子状态下，对一系列长达 12 个重复单元的低聚物进行了计算，结果用于推断两种聚合物在未掺杂和掺杂状态下的性质。此外，还在气相和乙腈溶液中估算了电子性质，后者溶剂用于两种导电聚合物的电生成。对结果的详细分析表明，尽管聚（3,4-亚乙基二氧噻吩）的π-π跃迁能在中性状态下低于聚（3,4-亚苯基二氧噻吩），但后者在 p 掺杂时表现为优良的电子导体。因此，氧化的聚（3,4-亚苯基二氧噻吩）显示出最低的π-π电子跃迁能。
