Surface Hopping within an Exciton Picture. An Electrostatic Embedding Scheme

• DOI: 10.1021/acs.jctc.8b00763
• Publication Date: 2018-10-09T19:16:56Z
• Authors: Maximilian F. S. ...; Felix Plasser; Benedetta Mennucci; Leticia González
• Keywords: 103006 Chemical physics; 104022 Theoretical chemistry; Computer Science Applications1707 Computer Vision and Pattern Recognition; Physical and Theoretical Chemistry; ELECTRONIC-ENERGY TRANSFER; LH2; PIGMENTS; COUPLINGS; 01 natural sciences; 7. Clean energy; 0104 chemical sciences; MODEL; CHARGE-TRANSFER; 104022 Theoretische Chemie; MOLECULAR-DYNAMICS; 103006 Chemische Physik; FIELD; NONADIABATIC DYNAMICS

We report the development and the implementation of an exciton approach that allows ab initio nonadiabatic dynamics simulations of electronic excitation energy transfer in multichromophoric systems. For the dynamics, a trajectory-based strategy is used within the surface hopping formulation. The approach features a consistent hybrid formulation that allows the construction of potential energy surfaces and gradients by combining quantum mechanics and molecular mechanics within an electrostatic embedding scheme. As an application, the study of a molecular dyad consisting of a covalently bound BODIPY moiety and a tetrathiophene group is presented using time-dependent density functional theory (TDDFT). The results obtained with the exciton model are compared to previously performed full TDDFT dynamics of the same system. Our results show excellent agreement with the full TDDFT results, indicating that the couplings that lead to excitation energy transfer (EET) are dominated by Coulomb interaction terms and that charge-transfer states are not necessary to properly describe the nonadiabatic dynamics of the system. The exciton model also reveals ultrafast coherent oscillations of the excitation between the two units in the dyad, which occur during the first 50 fs.