Xu Chao, Lin Congru, Peng Jiawei, Zhang Juanjuan, Lin Shichen, Gu Feng Long, Gelin Maxim F, Lan Zhenggang
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education and Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety; School of Environment, South China Normal University, Guangzhou 510006, People's Republic of China.
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-Park, Fukuoka 816-8580, Japan.
J Chem Phys. 2024 Mar 14;160(10). doi: 10.1063/5.0201204.
We combine on-the-fly trajectory surface hopping simulations and the doorway-window representation of nonlinear optical response functions to create an efficient protocol for the evaluation of time- and frequency-resolved fluorescence (TFRF) spectra and anisotropies of the realistic polyatomic systems. This approach gives the effective description of the proper (e.g., experimental) pulse envelopes, laser field polarizations, and the proper orientational averaging of TFRF signals directly from the well-established on-the-fly nonadiabatic dynamic simulations without extra computational cost. To discuss the implementation details of the developed protocol, we chose cis-azobenzene as a prototype to simulate the time evolution of the TFRF spectra governed by its nonadiabatic dynamics. The results show that the TFRF is determined by the interplay of several key factors, i.e., decays of excited-state populations, evolution of the transition dipole moments along with the dynamic propagation, and scaling factor of the TFRF signals associated with the cube of emission frequency. This work not only provides an efficient and effective approach to simulate the TFRF and anisotropies of realistic polyatomic systems but also discusses the important relationship between the TFRF signals and the underlining nonadiabatic dynamics.
我们将实时轨迹表面跳跃模拟与非线性光学响应函数的门道-窗口表示相结合，以创建一种有效的方法来评估实际多原子系统的时间分辨和频率分辨荧光（TFRF）光谱及各向异性。这种方法直接从成熟的实时非绝热动力学模拟中，无需额外计算成本，就能有效描述合适的（如实验中的）脉冲包络、激光场偏振以及TFRF信号的适当取向平均。为了讨论所开发方法的实现细节，我们选择顺式偶氮苯作为原型，来模拟由其非绝热动力学控制的TFRF光谱的时间演化。结果表明，TFRF由几个关键因素的相互作用决定，即激发态布居的衰减、跃迁偶极矩随动态传播的演化以及与发射频率立方相关的TFRF信号的比例因子。这项工作不仅提供了一种有效模拟实际多原子系统的TFRF和各向异性的方法，还讨论了TFRF信号与潜在非绝热动力学之间的重要关系。
