The Radiative Surface Hopping (RSH) algorithm: capturing fluorescence events in molecular systems within a semi-classical Non-Adiabatic Molecular Dynamics framework

21 December 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

In this article, we present the Radiative Surface Hopping (RSH) algorithm which enables to model fluores- cence within a semi-classical Non-Adiabatic Molecular Dynamics framework. The algorithm has been tested for the photodeactivation dynamics of trans-4-Dimethylamino-4’-cyanostilbene (DCS). By treating on equal footing radiative and non-radiative processes, our method allows to attain a complete molecular movie of the excited-state deactivation. Our dynamics rely on a semiempirical quantum mechanical/molecular mechanical (QM/MM) Hamiltonian and has been run for hundreds of picoseconds, both in the gas phase and in isopropyl ether. The proposed approach successfully captures the first fluorescence processes occurring in DCS and it suc- ceeds in reproducing the experimental fluorescence lifetime and quantum yield, especially in the polar solvent. The analysis of the geometrical features of the emissive species during the dynamics discards the hypothesis of a twisted intramolecular charge transfer (TICT) state to be responsible for the dual emission observed experimen- tally in some polar solvents. In a nutshell, our method opens the way for theoretical studies on early-fluorescence events occurring up to hundreds of picoseconds in molecular systems.

Keywords

photochemistry
non-adiabatic molecular dynamics
fluorescence

Supplementary materials

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Supporting Information
Description
The Supporting Information of this article contains the fol- lowing data: geometrical features of the optimized DCS S0 structure (Sec. (1)), detailed information about the QM/MM system preparation (Sec. (2)), results of the convergence tests for the thermalization trajectories in both gas phase and iso- propyl ether (Sec. (3)), results for gas phase trajectories with- out making use of the energy difference threshold correction for the non-radiative transitions (Sec. (4)), the description of the penalty function to search conical intersections as imple- mented in MOPAC (Sec. (5)), the molecular structures of the S1-S0 conical intersection found and those corresponding to the S1 local minima (Sec. (6)), the application of a first-order kinetic model to describe the S1 population for the corrected gas phase trajectories (Sec. (7)) and the variation of the S1- manuscript. S0 energy difference along the simulations in isopropyl ether (Sec. (8)).
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