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Non-adiabatic molecular dynamics of PAH-related complexes

Abstract : Polycyclic Aromatic Hydrocarbons (PAHs) have been proposed as main carriers of diffuse interstellar bands that are observed in the interstellar medium. This has motivated an extensive study of their photophysical and photochemical response to UV irradiation. Underlying competing mechanisms drive the evolution of gas in the interstellar medium. The main objective of this thesis is to describe and to get theoretical insight in the energy relaxation mechanisms in large PAH molecules via extensive non-adiabatic molecular dynamics simulations coupled to the linear response Time-Dependent Density Functional based Tight Binding (TD-DFTB) approach of the excited states. Prerequisite substantial development was made in the DFTB deMon-Nano package (, firstly with the implementation of analytical gradients of potential energy surfaces (PESs) and of non-adiabatic couplings within the TD-DFTB scheme. Next, the Tully's fewest-switches trajectory surface hopping (FSSH) algorithm has been adapted and coupled to the TD-DFTB scheme in order to take into account non-adiabatic transitions. After detailed methodological considerations and comparison with higher-level electronic structure methods, the first full-scale application is dedicated to non-adiabatic molecular dynamics of linearly cata-condensed PAHs. Electronic relaxation from the brightest excited state has been simulated for neutral polyacenes with 2 to 7 aromatic cycles. The results display a striking alternation in decay times of the brightest singlet state computed for polyacenes with up to 6 aromatic cycles, which is correlated with a qualitatively similar alternation of energy gaps between the brightest state and the state lying just below in energy. Next, the influence of geometry on relaxation has been investigated through the comparison of two isomers: armchair-edge chrysene versus zigzag-edge tetracene. After assessing the performance of DFTB parameter sets, the main focus is given to the analysis of the electronic relaxation from the brightest excited state, which is located around 270 nm for both isomers. The results show that the electronic population of the brightest excited state in chrysene decays an order-of-magnitude faster than that in tetracene. This is correlated with a significant difference in energy gaps between the brightest state and the state lying just below in energy, which is consistent with the previous conclusions for polyacenes. A last major development concerns the use of Machine Learning (ML) algorithms that have been proposed as a way to avoid most of the computationally-demanding electronic structure calculations. It aims to assess the performance of neural networks algorithms applied to excited-state dynamics. Electronic relaxation in neutral phenanthrene has been chosen as a test case due to the diversity of available experimental results. Several neural networks have been trained with different parameters and their respective accuracy and efficiency analyzed. In addition, approximate trajectory surface hopping schemes have been interfaced to ML-based PESs and gradients, resulting in non-adiabatic dynamics simulations at a negligible cost. Various simplified hopping approaches have been compared with FSSH. Overall, ML is found to be a highly promising tool for nanosecond-long molecular dynamics in excited states. This PhD research opens new avenues to investigate theoretical photophysics of large molecular complexes. Last but not least, the theoretical tools developed and implemented in deMon-Nano in a modular way can be further combined with other advanced (such as Configuration Interaction) DFTB techniques better adapted to charge-transfer states.
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Submitted on : Tuesday, January 5, 2021 - 5:57:50 PM
Last modification on : Wednesday, January 6, 2021 - 3:43:33 AM


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  • HAL Id : tel-02983135, version 2


Evgeny Posenitskiy. Non-adiabatic molecular dynamics of PAH-related complexes. Physics [physics]. Université Paul Sabatier - Toulouse III, 2020. English. ⟨NNT : 2020TOU30080⟩. ⟨tel-02983135v2⟩



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