We report the formulation and implementation of an extended Frenkel exciton model (EFEM) designed for simulating the dynamics of multichromophoric systems, taking into account the possible presence of interchromophore charge transfer states, as well as other states in which two chromophores are simultaneously excited. Our approach involves constructing a Hamiltonian based on calculations performed on monomers and selected dimers within the multichromophoric aggregate. Nonadiabatic molecular dynamics is addressed using a surface hopping approach, while the electronic wave functions and energies required for constructing the EFEM are computed utilizing the semiempirical floating occupation molecular orbitals-configuration interaction (FOMO-CI) electronic structure method. To validate our approach, we simulate the singlet fission process in a trimer of 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene (ThBF) molecules, embedded in their crystal environment, comparing the results of the EFEM to the standard “supermolecule” approach.

中文翻译：

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非绝热动力学的激子方法：超越 Frenkel 激子模型


我们报道了扩展 Frenkel 激子模型 （EFEM） 的制定和实施，该模型旨在模拟多发色团系统的动力学，同时考虑到可能存在的色间电荷转移态，以及两个发色团同时激发的其他状态。我们的方法涉及根据对多色团聚集体内的单体和选定二聚体进行的计算来构建哈密顿量。非绝热分子动力学使用表面跳跃方法解决，而构建 EFEM 所需的电子波函数和能量则利用半经验浮动占用分子轨道-构型相互作用 （FOMO-CI） 电子结构方法计算。为了验证我们的方法，我们模拟了嵌入其晶体环境中的 2,5-双（芴-9-亚基）-2,5-二氢噻吩 （ThBF） 分子三聚体中的单线态裂变过程，将 EFEM 的结果与标准的“超分子”方法进行比较。