AI 中文总结
该研究提出基于Wannier轨道的瞬态极化子局域化框架，用于晶态π共轭聚合物的定量电荷输运模拟，验证了其对萘二酰亚胺-联噻吩共聚物的适用性，揭示了链间相干性的关键作用，为相关材料输运机制研究提供了可迁移方法。
AI 中文摘要
晶态π共轭聚合物的定量电荷输运建模需要一种电子表征方法，该方法需同等捕捉延伸共轭效应和材料特有的电子-声子相互作用。我们提出了基于Wannier轨道的瞬态极化子局域化（TPL）框架公式，用于晶态π共轭聚合物的定量电荷输运模拟。通过直接将所有相互作用表达为从第一性原理计算得到的Wannier表示，该方法避免了聚合物主链的人为碎片化，且能对电子耦合和电子-声子相互作用进行一致的、材料特有的描述。在模式分辨的TPL形式体系中纳入了低频和高频振动模式，得到了有效电子哈密顿量，可同时捕捉动态无序和极化子重整化。该方法在 ambipolar 晶态萘二酰亚胺-联噻吩共聚物上得到验证，可直接比较沿聚合物主链和π堆积方向的电子与空穴输运。模拟重现了关键输运特征，包括显著的各向异性以及电子迁移率高于空穴迁移率。对单链和双链体系的额外研究揭示了链间相干性在支撑沿聚合物主链的高效输运中的关键作用。除该特定体系外，基于Wannier轨道的TPL框架为解析晶态π共轭材料的本征电荷输运机制提供了可迁移的途径，并为后续研究奠定了基础。
英文摘要
Quantitative charge-transport modelling in crystalline pi-conjugated polymers requires an electronic representation that captures extended conjugation and material-specific electron-phonon interactions on equal footing. We present a Wannier-orbital-based formulation of the transient-polaron-localization (TPL) framework for quantitative charge-transport simulations in crystalline pi-conjugated polymers. By expressing all interactions directly in a Wannier representation derived from first-principles calculations, the approach avoids artificial fragmentation of polymer backbones and enables a consistent, material-specific description of electronic couplings and electron-phonon interactions. Low- and high-frequency vibrational modes are incorporated within a mode-resolved TPL formalism, yielding an effective electronic Hamiltonian that captures both dynamic disorder and polaronic renormalization. The methodology is demonstrated for the ambipolar crystalline naphthalenediimide-bithiophene copolymer, enabling a direct comparison of electron and hole transport along the polymer backbone and pi-stacking directions. The simulations reproduce key transport features, including pronounced anisotropy and higher electron than hole mobility. Additional studies on single- and bi-chain systems reveal the essential role of inter-chain coherence in supporting efficient transport along the polymer backbone. Beyond this specific system, the Wannier-orbital-based TPL framework provides a transferable route to disentangle intrinsic charge-transport mechanisms in crystalline pi-conjugated materials and establishes a foundation for future work.
