Phosphorescence is a phenomenon of delayed luminescence that corresponds to the radiative decay of the molecular triplet state. As a general property of molecules, phosphorescence represents a cornerstone problem of chemical physics due to the spin prohibition of the underlying triplet-singlet emission and because its analysis embraces a deep knowledge of electronic molecular structure. Phosphorescence is the simplest physical process which provides an example of spin-forbidden transformation with a characteristic spin selectivity and magnetic field dependence, being the model also for more complicated chemical reactions and for spin catalysis applications. The bridging of the spin prohibition in phosphorescence is commonly analyzed by perturbation theory, which considers the intensity borrowing from spin-allowed electronic transitions. In this review, we highlight the basic theoretical principles and computational aspects for the estimation of various phosphorescence parameters, like intensity, radiative rate constant, lifetime, polarization, zero-field splitting, and spin sublevel population. Qualitative aspects of the phosphorescence phenomenon are discussed in terms of concepts like structure–activity relationships, donor–acceptor interactions, vibronic activity, and the role of spin–orbit coupling under charge-transfer perturbations. We illustrate the theory and principles of computational phosphorescence by highlighting studies of classical examples like molecular nitrogen and oxygen, benzene, naphthalene and their azaderivatives, porphyrins, as well as by reviewing current research on systems like electrophosphorescent transition metal complexes, nucleobases, and amino acids. We furthermore discuss modern studies of phosphorescence that cover topics of applied relevance, like the design of novel photofunctional materials for organic light-emitting diodes (OLEDs), photovoltaic cells, chemical sensors, and bioimaging.

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磷光现象的理论与计算

磷光是一种延迟发光的现象，与分子三重态的辐射衰减相对应。作为分子的一般属性，磷光是化学物理学的基石问题，这是由于潜在的三重态-单重态发射的自旋禁止以及其分析包含了对电子分子结构的深入了解。磷光是最简单的物理过程，提供了具有自旋选择性和磁场依赖性的自旋禁变的示例，它也是更复杂的化学反应和自旋催化应用的模型。通常用摄动理论分析磷光中自旋禁止的桥接，该理论考虑了自旋允许的电子跃迁的强度借用。在这篇综述中，我们着重介绍了估算各种磷光参数的基本理论原理和计算方面，例如强度，辐射速率常数，寿命，极化，零场分裂和自旋子能级。从结构-活性关系，供体-受体相互作用，电子振动以及自旋-轨道耦合在电荷转移扰动下的作用等概念对磷光现象的定性方面进行了讨论。我们通过重点介绍分子氮和氧，苯，萘及其氮杂衍生物，卟啉等经典实例的研究，并回顾当前对电致磷光过渡金属配合物，核碱基等系统的研究，来说明计算磷光的理论和原理。和氨基酸。我们还将讨论涉及应用相关主题的现代磷光研究，例如用于有机发光二极管（OLED），光伏电池，化学传感器和生物成像的新型光功能材料的设计。