Predicting Phosphorescence Rates of Light Organic Molecules Using Time-Dependent Density Functional Theory and the Path Integral Approach to Dynamics
Predicting Phosphorescence Rates of Light Organic Molecules Using Time-Dependent Density Functional Theory and the Path Integral Approach to Dynamics
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DOI：
10.1021/acs.jctc.8b00841
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发表时间：
2019-03-01
影响因子：
5.5
通讯作者：
Izsak, Robert
中科院分区：
文献类型：
--
作者：
de Souza, Bernardo;Farias, Giliandro;Izsak, Robert
在这项工作中，我们提出了一个一般的方法来预测磷光率和光谱的分子使用含时密度泛函理论（TD-DFT）和路径积分的方法，依赖于谐振子近似的核运动的动力学。我们首先讨论了单重态和三重态激发态之间的自旋轨道耦合（SOC）的理论，然后讨论了如何计算校正的跃迁偶极矩和磷光率。我们调查的依赖这些速率上的一些TD-DFT参数，如功能的性质，根的数量，和Tamm-Dancoff近似。在此之后，我们评估了不同的SOC积分方案的效果，并表明我们的最佳方法是适用于大量的系统具有不同的激发态特性。
In this work, we present a general method for predicting phosphorescence rates and spectra for molecules using time-dependent density functional theory (TD-DFT) and a path integral approach for the dynamics that relies on the harmonic oscillator approximation for the nuclear movement. We first discuss the theory involved in including spin-orbit coupling (SOC) among singlet and triplet excited states and then how to compute the corrected transition dipole moments and phosphorescence rates. We investigate the dependence of these rates on some TD-DFT parameters, such as the nature of the functional, the number of roots, and the Tamm-Dancoff approximation. After that, we evaluate the effect of different SOC integral schemes and show that our best method is applicable to a large number of systems with different excited state characters.