Sangiogo Gil Eduarda, Giustini Andrea, Accomasso Davide, Granucci Giovanni
Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, A-1090 Vienna, Austria.
Dipartimento di Chimica e Chimica Industriale, University of Pisa, 56124 Pisa, Italy.
J Chem Theory Comput. 2024 Oct 8;20(19):8437-8449. doi: 10.1021/acs.jctc.4c00886. Epub 2024 Sep 16.
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.
我们报告了一种扩展的弗伦克尔激子模型（EFEM）的构建和实施，该模型旨在模拟多发色团系统的动力学，同时考虑到发色团间电荷转移态以及两个发色团同时被激发的其他状态的可能存在。我们的方法包括基于对多发色团聚集体中的单体和选定二聚体进行的计算构建哈密顿量。使用表面跳跃方法处理非绝热分子动力学，而构建EFEM所需的电子波函数和能量则利用半经验浮动占据分子轨道-组态相互作用（FOMO-CI）电子结构方法进行计算。为了验证我们的方法，我们模拟了嵌入晶体环境中的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”方法的结果进行比较。
