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Reactivity of the Solvated Electron, the Hydroxyl Radical and Its Precursor in Deuterated Water Studied by Picosecond Pulse Radiolysis Furong Wang

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Reactivity of the Solvated Electron, the Hydroxyl Radical and Its Precursor in Deuterated Water Studied by Picosecond Pulse Radiolysis Furong Wang Reactivity of the Solvated Electron, the Hydroxyl Radical and its Precursor in Deuterated Water Studied by Picosecond Pulse Radiolysis Furong Wang To cite this version: Furong Wang. Reactivity of the Solvated Electron, the Hydroxyl Radical and its Precursor in Deuter- ated Water Studied by Picosecond Pulse Radiolysis. Theoretical and/or physical chemistry. Université Paris Saclay (COmUE), 2018. English. NNT : 2018SACLS399. tel-02057515 HAL Id: tel-02057515 https://tel.archives-ouvertes.fr/tel-02057515 Submitted on 5 Mar 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Reactivity of the Solvated Electron, the Hydroxyl Radical and its Precursor in Deuterated Water 2018SACLS399 : Studied by Picosecond Pulse NNT Radiolysis Thèse de doctorat de l'Université Paris-Saclay préparée à l'Université Paris-Sud École doctorale n°571 : sciences chimiques : molécules, matériaux instrumentation et biosystèmes (2MIB) Spécialité de doctorat : Chimie Thèse présentée et soutenue, le 22 Octobre, 2018, par Mme Furong WANG Composition du Jury : Mme Isabelle Lampre Professeur, Université Paris-Sud (– LCP) Présidente M. Jean-Marc Jung Professeur, Université de Strasbourg (– IPHC) Rapporteur M. Philippe Moisy Directeur de recherche, CEA Marcoule Rapporteur Mme Sophie Le Caer Directrice de recherche, CEA (– LIONS) Examinateur M. Khashayar Ghandi Professeur, University of Guelph Examinateur M. Mehran Mostafavi Professeur, Université Paris-Sud (– LCP) Directeur de thèse Acknowledgements Firstly, I would like to express my sincere gratitude to my advisor Prof. Mehran Mostafavi for the continuous support of my Ph.D study and related research, for his patience, motivation, and immense knowledge. His guidance helped me in all the time of research and writing of this thesis. I could not have imagined having a better advisor and mentor for my Ph.D study. Besides my advisor, I would like to thank the rest of my thesis committee: Prof. Jean-Marc Jung, Dr. Philippe Moisy, Dr. Sophie Le Caer, Prof. Isabelle Lampre and Prof. Khashayar Ghandi, for their insightful comments and encouragement, but also for the hard question which incented me to widen my research from various perspectives. I would like to thank Dr. Pascal Pernot, Dr. Pierre Archirel and Dr. Aurélien De Lande for their strong support, collaboration and insightful encouragement for my Ph.D research. Their excellent computation makes important sense to my thesis. My sincere thanks also goes to Prof. Jacqueline Belloni, Dr. Jean-Louis Marignier and Hydn Remita. Their personalities, curiosity to the science, the ways of thinking and performing research encouraged me to be a person Iike them. I would like to thank the engineers in our team, Dr. Uli Schmidhammer, Dr. Sergey Denisov, Jean- Philippe Larbre, Audrey Gayral, Pierre Jeunesse, Alexandre Demarque and Nicolas Decovemacher. Without them, I can’t perform experiments in ELYSE. I take this opportunity to express gratitude to all of administration group in the lab for helping me focusing the research, they are Séverine Bourguignon, Eve Ranvier, Anne Morel and Delphine Lelievre. I thank Mireille Benoit for careful arrangement of all the chemical compounds during my Ph.D. My sincere thanks also goes to my dear friends, Anna Balcerzyk, Jun Ma, Abdel Karim El Omar, Zhenpeng Cui, Xiaojing Wu, Xiaojiao Yuan, Viacheslav Shcherbakov, Raluca Musat, Teseer Bahry, Sarah Al-gharib…… I couldn’t put all their name on the list. We have good time through my four year’s life. I really enjoy the life here and never forget the memory in LCP. Last but not the least, I would like to thank my family: my parents and my sister. My study is always baked by their support. Université Paris Saclay—Sciences Chimiques : Molécules, Matériaux, Instrumentation et Biosystèmes Reactivity of the Solvated electron, the Hydroxyl radical and its Precursor in Deuterated Water Studied by Picosecond Pulse Radiolysis Chapter I: Introduction ............................................................................ 3 1.1 General introduction ....................................................................................... 3 1.2 Quantification of radiation ............................................................................. 4 1.2.1 Definition of linear energy transfer (LET) ....................................................................... 5 1.2.2 Definition of radiolytic yield ........................................................................................... 7 1.3 Radiolysis in water .......................................................................................... 8 1.3.1 Physical stage (<10-15 s) ................................................................................................... 9 1.3.2 Physicochemical stage (~10-15~10-12 s) ............................................................................ 9 1.3.3 Non-homogenous chemical stage (~10-12 -10-6 s) .......................................................... 11 1.4 Concluding remark ....................................................................................... 11 References ............................................................................................................ 13 Chapter II: Experimental methodology ................................................. 18 2.1 State of art ...................................................................................................... 18 2.1.1 High LET ....................................................................................................................... 18 2.1.2 Low LET ........................................................................................................................ 20 2.1.3 Detection technique for ultrafast radiolysis ................................................................... 25 2.2 ELYSE — A picosecond pump-probe radiolysis platform ....................... 27 2.2.1 EA-1 — Picosecond pulse-probe setup.......................................................................... 35 2.2.2 EA-3 — Streak camera .................................................................................................. 39 2.2.3 γ-source .......................................................................................................................... 46 2.3 SK-Ana — MCR-ALS analysis method ...................................................... 47 I Université Paris Saclay—Sciences Chimiques : Molécules, Matériaux, Instrumentation et Biosystèmes 2.4 Chemicals ....................................................................................................... 51 2.5 Concluding remark ....................................................................................... 52 References ............................................................................................................ 53 Chapter III: Time Dependent Yield of Solvated Electron and OD• Radical in Deuterated Water at Low LET Studied by Picosecond Pulse Radiolysis ................................................................................................. 59 3.1 State of the art and objective ....................................................................... 59 3.1.1 Introduction .................................................................................................................... 59 3.1.2 Objective ........................................................................................................................ 64 3.3 The solvated electron in D2O ........................................................................ 65 3.3.1 Isosbestic method ........................................................................................................... 67 3.3..2 Absorption spectrum of e ....................................................................................... 71 DO2 3.3.3 Determination of the time-dependent yield of ...................................................... 77 3.4 Time-dependent yield of OD• radical .......................................................... 81 3.4.1 Transient absorption induced in FSOFC ........................................................................ 82 3.4.2 Determination of the time-dependent yield of OD• radical ........................................... 90 3.5 Conclusions .................................................................................................... 92 Reference .............................................................................................................. 96 e Appendix: Molar absorption coefficient of s in D2O (250 to 1500 nm) obtained in the present work. ........................................................................... 101 Chapter IV: Ultra-fast Charge Migration Competes with Proton •+ Transfer in the Early Chemistry of H2O ........................................... 108 4.1 State of the art ............................................................................................. 108 II Université Paris Saclay—Sciences Chimiques : Molécules, Matériaux, Instrumentation et Biosystèmes
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