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Surface hopping within an exciton picture. An electrostatic embedding scheme

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journal contribution
posted on 2018-12-07, 15:13 authored by Maximilian F.S.J. Menger, Felix PlasserFelix Plasser, Benedetta Mennucci, Leticia Gonzalez
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.

Funding

M.F.S.J.M. gratefully acknowledges financial support from the EU Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 642294.

History

School

  • Science

Department

  • Chemistry

Published in

Journal of Chemical Theory and Computation

Volume

14

Issue

12

Pages

6139–6148

Citation

MENGER, M.F.S.J. ... et al, 2018. Surface hopping within an exciton picture. An electrostatic embedding scheme. Journal of Chemical Theory and Computation, 14(12), pp. 6139–6148.

Publisher

© American Chemical Society

Version

  • AM (Accepted Manuscript)

Publisher statement

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.8b00763

Acceptance date

2018-10-09

Publication date

2018-10-09

Copyright date

2018

ISSN

1549-9618

eISSN

1549-9626

Language

  • en

Location

United States

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