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Abstract：
This study explores the quantum size effects on the optical properties of pillar[n]arene (n = 5, 6, 7, 8) utilizing density functional theory (DFT) and wave function analysis. The mechanisms of electron transitions in one-photon absorption (OPA) and two-photon absorption (TPA) spectra are investigated, alongside the calculation of electron circular dichroism (ECD) for these systems. Transition Density Matrix (TDM) and electron-hole pair density maps are employed to study the electron excitation characteristics, unveiling a notable size dependency. Analysis of the transition electric dipole moment (TEDM) and the transition magnetic dipole moment (TMDM) reveals the electromagnetic interaction mechanism within pillar[n]arene. Raman spectra computations further elucidate vibrational modes, while interactions with external environments are studied using electrostatic potential (ESP) analysis, and electron delocalization is assessed under an external magnetic field, providing insights into the magnetically induced current phenomena within these supramolecular structures. The thermal stability of pillar[n]arene was investigated by ab initio molecular dynamics (AIMD).
摘要：
本研究利用密度泛函理论（DFT）和波函数分析探讨了量子尺寸对[n]芳烃（n=5、6、7、8）光学性质的影响。研究了单光子吸收（OPA）和双光子吸收（TPA）光谱中的电子跃迁机理，以及这些系统的电子圆二色性(ECD)的计算。过渡密度矩阵（TDM）和电子-空穴对密度图用于研究电子激发特性，揭示了一个值得注意的大小依赖关系。对跃迁电偶极矩（TEDM）和跃迁磁偶极矩（TMDM）的分析揭示了柱[n]芳烃内部的电磁相互作用机制。拉曼光谱计算进一步阐明振动模式，在使用静电势(ESP)分析研究与外部环境的相互作用时，在外部磁场下评估电子离域，提供对这些超分子结构中磁感应电流现象的见解。通过从头算分子动力学（AIMD）研究了柱[n]芳烃的热稳定性。
