大学化学 >> 2026, Vol. 41 >> Issue (6): 374-384.doi: 10.12461/PKU.DXHX202507082

化学实验 上一篇    

有机长余辉分子三重态寿命和磷光辐射速率的理论计算——介绍一个计算化学综合实验

郑超, 孙诚希, 陈润锋   

  1. 南京邮电大学材料科学与工程学院, 江苏 南京 210023
  • 收稿日期:2025-07-21 录用日期:2025-09-09 发布日期:2026-06-18
  • 通讯作者: 陈润锋 E-mail:iamrfchen@njupt.edu.cn Runfeng Chen
  • 基金资助:
    南京邮电大学教改项目(JG03014JX58)；国家自然科学基金项目(62374093, 22275097, 62288102)

Theoretical calculations of triplet state lifetimes and phosphorescence radiative rates in organic long-persistent luminescence molecules: Introducing a comprehensive computational chemistry experiment

Chao Zheng, Chengxi Sun, Runfeng Chen   

  1. Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, Jiangsu Province, China
  • Received:2025-07-21 Accepted:2025-09-09 Published:2026-06-18
  • Contact: Runfeng Chen E-mail:iamrfchen@njupt.edu.cn

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摘要： 有机长余辉发光材料在撤去激发源后仍可持续发光，表现出独特的光物理性质，在光电器件、柔性显示、信息加密及生物成像等领域具有广阔的应用前景。有机长余辉性能高度依赖于三重态激子的寿命及磷光辐射速率等关键参数，传统实验手段难以精准解析微观有机分子电子结构与宏观发光行为之间的构效关系，而计算化学方法为揭示其内在机制提供了重要途径。本实验以典型有机小分子吩噻嗪体系长余辉材料为研究对象，采用密度泛函理论优化基态与激发态几何构型，并计算自旋轨道耦合常数，结合含时密度泛函理论评估能级跃迁特性及辐射衰减通道，揭示有机分子三线态寿命与长余辉发光辐射速率等之间的内在关系。通过将前沿研究成果转化为教学资源，本实验有效提升了学生对激发态动力学与材料性能关联机制的理解，为计算化学课程提供了兼具学术深度与应用价值的有益探索。

关键词: 计算化学, 有机长余辉, 超长有机磷光, 自旋轨道耦合, 三重态激子, 磷光辐射速率, 教学研究

Abstract: Organic long-persistent luminescent materials exhibit unique photophysical properties by sustaining light emission after excitation removal, demonstrating broad application potential in optoelectronic devices, flexible displays, information encryption, and bioimaging. The long-afterglow performance critically depends on key parameters including triplet exciton lifetime and phosphorescence radiative rate. While conventional experimental approaches face challenges in precisely elucidating the structure-property relationships between microscopic molecular electronic structures and macroscopic luminescent behaviors, computational chemistry methods offer powerful tools to uncover the underlying mechanisms. This study investigates a representative phenothiazine-based organic small-molecule system with long-persistent luminescence. Using density functional theory (DFT), we optimized both ground-state and excited-state geometries and calculated spin-orbit coupling constants. Through time-dependent DFT (TD-DFT) calculations, we evaluated energy-level transition characteristics and radiative decay pathways, thereby revealing the intrinsic correlation between molecular triplet-state lifetimes and long-afterglow radiative rates. By translating cutting-edge research into pedagogical resources, this experiment significantly enhances students’ comprehension of excited-state dynamics and material property relationships, providing a valuable case study for computational chemistry courses that combines academic rigor with practical applications.

Key words: Computational chemistry, Organic long-persistent luminescence, Ultralong organic phosphorescence, Spin-orbit coupling, Triplet exciton, Phosphorescence radiative rate, Teaching-oriented research