In this work, the electronic properties of a substituted polypyrrole (PPy−R) deposited on a palladium–fullerene polymer (C₆₀Pd₂(‐2Pd)) were obtained by first principles DFT+vdW calculations. By introducing both electron‐withdrawing (COOH) and electron‐donating (NH₂) substituents into the polypyrrole chain, we modulated the HOMO and LUMO levels of PPy−R/C₆₀Pd₂(‐2Pd). Furthermore, we also determined the influence of the second COOH group in each pyrrole ring and the CH₃ group linked to the nitrogen atom on the electronic properties. The calculated data show that the type of substituent, as well as the termination of the palladium–fullerene polymer, strongly influences the band gap. The general picture of the mixed systems reveals that the HOMO corresponds to that of PPy/PPy−R and the LUMO corresponds to that of C₆₀Pd₂(‐2Pd). For isolated PPy−R, the substituent strongly influences the relative position of the HOMO and LUMO levels toward the vacuum level, and, based on this fact, we can easily tune the band gap of the mixed systems. For the sake of completeness, all configurations, as well as the corresponding total binding energies, were carefully analysed and compared. The adsorption of PPy(‐R) on the Pd‐terminated C₆₀Pd₂ led to the formation of surface Py⋅⋅⋅Pd complexes that have higher binding energies than in the case of the C₆₀‐terminated polymer. Furthermore, composites with two PPy chains on C₆₀Pd₂ (‐2Pd) were also studied.

中文翻译：

---

聚吡咯衍生物和C60Pd3聚合物作为p–n结模型的带隙调整：第一原理计算研究

在这项工作中，通过第一原理DFT + vdW计算获得了沉积在钯-富勒烯聚合物（C ₆₀ Pd ₂（-2Pd））上的取代聚吡咯（PPy-R）的电子性能。通过在聚吡咯链中同时引入吸电子（COOH）和给电子（NH ₂）取代基，我们调节了PPy-R / C ₆₀ Pd ₂（-2Pd）的HOMO和LUMO含量。此外，我们还确定了每个吡咯环和CH _3中第二个COOH基团的影响基团与氮原子上的电子性质相连。计算数据表明，取代基的类型以及钯-富勒烯聚合物的端基对带隙有很大影响。混合系统的总体图显示，HOMO对应于PPy / PPy-R，而LUMO对应于C ₆₀ Pd ₂（-2Pd）。对于分离的PPy-R，取代基强烈影响HOMO和LUMO能级相对于真空能级的相对位置，基于此事实，我们可以轻松地调整混合系统的带隙。为了完整起见，仔细分析和比较了所有构型以及相应的总结合能。PPy（‐R）在Pd终止的C ₆₀ Pd上的吸附₂导致表面Py·⋅·Pd络合物的形成，其结合能比C ₆₀端基聚合物高。此外，还研究了在C ₆₀ Pd ₂（-2Pd）上具有两条PPy链的复合材料。