رسالة جامعية
Quantum dynamics of electron tranfer in strongly coupled environments ; Dynamique quantique de transferts d'électron dans des systèmes environnés à fort couplage
| العنوان: | Quantum dynamics of electron tranfer in strongly coupled environments ; Dynamique quantique de transferts d'électron dans des systèmes environnés à fort couplage |
|---|---|
| المؤلفون: | Mangaud, Etienne |
| المساهمون: | Théorie (LCAR), Laboratoire Collisions Agrégats Réactivité (LCAR), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université Paul Sabatier - Toulouse III, Christoph Meier, Michèle Desouter-Lecomte |
| المصدر: | https://hal.science/tel-01401868Test ; Chimie théorique et/ou physique. Université Paul Sabatier - Toulouse III, 2016. Français. ⟨NNT : 2016TOU30077⟩. |
| بيانات النشر: | HAL CCSD |
| سنة النشر: | 2016 |
| المجموعة: | Université Toulouse III - Paul Sabatier: HAL-UPS |
| مصطلحات موضوعية: | Electron transfer, Quantum dynamics, Dissipative quantum methods, Multidimensional quantum methods, Hierarchical equations of motion (HEOM), Hetero junction, Mixed-valence organic compounds, Cryptochrome, Transferts d'électron, Matrices hiérarchiques (HEOM), Dynamique quantique, Hétérojonction, Méthodes quantiques dissipatives, Composés organiques à valence mixte, Méthodes quantiques multidimensionnelles, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry |
| الوصف: | Electron transfer reactions are at stake in several chemical, biological or photochemical processes of great interest as, for instance, photovoltaic technology or photosynthesis where they are rarely isolated. Furthermore, experimental results show that quantum phenomena, notably superpositions of states or coherences, can persist on the time scale of the electron transfer even in the presence of an environment. In this work, electron transfer is studied in three types of molecular systems. The first one is an intermolecular transfer in an oligothiophene-fullerene heterojonction modelling a charge separation interface for future organic photovoltaic devices. The second one is an intramolecular transfer in mixed-valence organic compounds where the bridge effect of an increasing n-paraphenylens chain is studied on aromatic polymers with donor-acceptor sites (1-4,dimethoxy-3-methylphenylens). The third one is an intermolecular transfer in a tryptophan chain of a cryptochrome chromoprotein. In all these cases, a special attention is given to realistic modelling. In this context, it is crucial to define carefully the partition between the degrees of freedom, in particular amongst those implied in the transfer and those qualified to be part of an environment. To this end, a Hamiltonian describing a donor-acceptor electronic system coupled to a bath of harmonic oscillators is parameterized using the constrained DFT method (cDFT). The oscillators' bath is described by a normal mode analysis or via the electronic gap fluctuation obtained by QM/MM calculations. The systems under study turn out to be strongly coupled, and structured which requires to explore non-conventional strategies. In a model environment constituted of a finite number of oscillators treated explicitly, the dynamics is performed by multidimensional quantum propagation methods such as the multi-layer multiconfigurational time-dependent Hartree method (ML-MCTDH). In the dissipative approach, where the bath acts only by its statistical properties, it is ... |
| نوع الوثيقة: | doctoral or postdoctoral thesis |
| اللغة: | French |
| العلاقة: | NNT: 2016TOU30077; tel-01401868; https://hal.science/tel-01401868Test; https://hal.science/tel-01401868v3/documentTest; https://hal.science/tel-01401868v3/file/Th%C3%A8se%20EM%2026072017.pdfTest |
| الإتاحة: | https://hal.science/tel-01401868Test https://hal.science/tel-01401868v3/documentTest https://hal.science/tel-01401868v3/file/Th%C3%A8se%20EM%2026072017.pdfTest |
| حقوق: | info:eu-repo/semantics/OpenAccess |
| رقم الانضمام: | edsbas.D3946057 |
| قاعدة البيانات: | BASE |
| الوصف غير متاح. |