This research explores the electronic properties and conformational dynamics of the ZnP‐COPV‐ (Zinc Porphyrin ‐ Carbon bridged Oligo Phenylenevinylene ‐ Fullerene) organic semiconductor via specialized Density Functional Theory (DFT) and Molecular Dynamics (MD) computational techniques. First, through DFT calculations, essential HOMO (Highest Occupied Molecular Orbital), LUMO (Lowest Unoccupied Molecular Orbital), and Molecular Electrostatic Potential (MEP) electronic attributes are meticulously dissected providing insights into the intricate charge transfer processes between the constituent donor‐acceptor moieties. Furthermore, MD simulations are employed to unveil the molecular system's multifaceted conformational flexibility and stability. The Root‐mean‐squared deviation (RMSD), end‐to‐end distance, and torsional angles quantitative analysis of conformational attributes support the carbon‐bridged oligo‐phenylenevinylene (COPV) molecular wire's ‐skeleton planar and rigid conformation. This minimal end‐to‐end distance variation (within Å) compared to the initially extended structure and the constrained torsional motion (within for ZnP‐COPV and for COPV‐) after thermalization showcases COPV's ability to maintain structural rigidity over time, aligning with the concept of effective ‐conjugation. Finally, through the lens of time dependent (TD)‐DFT, the dynamic evolution of the HOMO–LUMO energy gap, TD‐DFT excitation energies and oscillator strengths are explored as the molecular structure transforms over time. The observed energy gap variation underscores the molecule's adaptability in the face of structural modifications, hinting at an intriguing connection between structural stability and enhanced electronic properties. The research provides a comprehensive understanding of the intricate interplay between conformational dynamics and electronic attributes in organic semiconductors, providing quantitative insights crucial for designing stable, high‐performance materials for cutting‐edge optoelectronic applications and helping advance the collective understanding of sustainable energy conversion.

中文翻译：

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探索有机供体-桥-受体分子系统的电子和构象属性


本研究通过专门的密度泛函理论 （DFT） 和分子动力学 （MD） 计算技术，探索了 ZnP‐COPV‐（锌卟啉 ‐ 碳桥寡核苷酸苯乙烯基 ‐ 富勒烯）有机半导体的电子特性和构象动力学。首先，通过 DFT 计算，仔细剖析基本的 HOMO（最高占用分子轨道）、LUMO（最低未占用分子轨道）和分子静电势 （MEP） 电子属性，从而深入了解组成供体-受体部分之间错综复杂的电荷转移过程。此外，采用 MD 模拟来揭示分子系统的多方面构象灵活性和稳定性。构象属性的均方根偏差 （RMSD）、端到端距离和扭转角定量分析支持碳桥寡苯乙烯 （COPV） 分子线的骨架平面和刚性构象。与最初延伸的结构和热化后的约束扭转运动（ZnP-COPV 和 COPV-的内）相比，这种最小的端到端距离变化（在 Å 内）展示了 COPV 随着时间的推移保持结构刚度的能力，与有效共轭的概念一致。最后，通过时间依赖性 （TD）-DFT 的视角，随着分子结构随时间的变化，探索了 HOMO-LUMO 能隙、TD-DFT 激发能和振荡器强度的动态演变。观察到的能隙变化强调了分子在面对结构修饰时的适应性，暗示了结构稳定性和增强的电子特性之间的有趣联系。 该研究全面了解有机半导体中构象动力学和电子属性之间错综复杂的相互作用，为为尖端光电应用设计稳定、高性能的材料提供了至关重要的定量见解，并有助于促进对可持续能源转换的集体理解。