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Development and Application of Methods Based on Extremely Localized Molecular Orbitals Benjamin Meyer

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Development and Application of Methods Based on Extremely Localized Molecular Orbitals Benjamin Meyer Development and application of methods based on extremely localized molecular orbitals Benjamin Meyer To cite this version: Benjamin Meyer. Development and application of methods based on extremely localized molecular orbitals. Theoretical and/or physical chemistry. Université de Lorraine, 2016. English. NNT : 2016LORR0179. tel-01526689 HAL Id: tel-01526689 https://tel.archives-ouvertes.fr/tel-01526689 Submitted on 23 May 2017 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. AVERTISSEMENT Ce document est le fruit d'un long travail approuvé par le jury de soutenance et mis à disposition de l'ensemble de la communauté universitaire élargie. Il est soumis à la propriété intellectuelle de l'auteur. Ceci implique une obligation de citation et de référencement lors de l’utilisation de ce document. D'autre part, toute contrefaçon, plagiat, reproduction illicite encourt une poursuite pénale. Contact : [email protected] LIENS Code de la Propriété Intellectuelle. articles L 122. 4 Code de la Propriété Intellectuelle. articles L 335.2- L 335.10 http://www.cfcopies.com/V2/leg/leg_droi.php http://www.culture.gouv.fr/culture/infos-pratiques/droits/protection.htm Thèse en vue de l’obtention du grade de Docteur de l’Université de Lorraine Mention Chimie Development and Application of Methods Based on Extremely Localized Molecular Orbitals Benjamin MEYER École Doctorale SESAMES Collegium Sciences et Technologies Laboratoire Structure et Réactivité des Systèmes Moléculaires Complexes Thèse présentée et soutenue publiquement le 10 Octobre 2016 Composition du Jury Rapporteurs : Arianna Fornili Research Fellow University of London Simon Grabowsky Professor University of Bremen Examinateurs : Julia Contreras-Garcia Chargé de recherche Université Pierre et Marie Curie Benoit Guillot Professeur Université de Lorraine Directeur de thèse Manuel Ruiz-Lopez Directeur de recherche Université de Lorraine Co-directeur de thèse Alessandro Genoni Chargé de recherche Université de Lorraine i À Justine À ma famille Acknowledgements/Remerciements At first, I would like to express my gratitude to the jury members who have accepted to evaluate this manuscript. I am especially grateful to Prof. Arianna Fornili and Simon Grabowsky for hav- ing reviewed this work. Je tiens à remercier très chaleureusement les docteurs Manuel Ruiz-Lopez et Alessandro Genoni pour leur accompagnement et leur soutien. J’ai vraiment eu la chance de travailler avec deux di- recteurs de thèse très complémentaires qui m’ont appris énormément de choses durant ces 3 années. Ce manuscrit est le fruit de leur constante disponibilité à répondre à mes nombreuses sollicitations. Merci à tous les deux pour votre gentillesse, votre patience et pour ces beaux moments partagés. Je souhaite remercier tous les membres permanents et non-permanents du Laboratoire SRSMC pour m’avoir permis de travailler dans une ambiance chaleureuse. Il m’est malheureusement im- possible d’être exhaustif, mais j’aimerais particulièrement remercier le professeur Jean-Louis Ri- vail avec qui ce fut toujours un plaisir de discuter lors de ses visites au laboratoire ainsi que le professeur Xavier Assfeld pour tous ces formidables moments passés ensemble. Mes pensées vont également vers les professeurs Gérald Monard, Claude Millot, Ugo Ancarani, Claude Dal Cappelo, Jean-Bernard Regnouf de Vains ainsi que les docteurs Mariachiara Pastore Franscesca Ingrosso, Alexandrine Lambert, Marilia Martins-Costa, Nadia Canhilo, Andreea Pasc, Antonio Monari, Sébastien Lebègue, Christophe Chipot, François Dehez, Mounir Tarek, Fabien Pascale, Arnaud Leclerc... J’aimerais également remercier tous membres du laboratoire CITHEFOR pour leur accueil et leur disponibilité durant mes trois années de monitorat à la faculté de pharmacie. Je tiens tout par- ticulièrement à remercier les professeurs Pierre Leroy et Igor Clarot ainsi que les docteurs Ariane Boudier, Caroline Gaucher et Marianne Parent pour leur sympathie et tous les excellents moments passés à les écouter discuter de galénique, culture cellulaire ou d’expérimentations animales. De plus, ce fut un réel plaisir de collaborer avec cette équipe lors de projets en marge de mon travail principal qui sera exposé dans ce manuscrit. iv J’aimerais aussi exprimer mes sincères reconnaissances à un bon nombre de personnes qui m’auront soutenu tant humainement que scientifiquement : Philippe Gros, Marco Marazzi, Julian Garrec, Oleksandr Loboda, Yann Cornaton, Julien Eng, Tim Krah, Alex Domingo, Pierre-François Loos, Yohann Moreau, Philippe Carbonnière, Maura Casciola, Marina Kasimova, Audrey, Pablo, Grace, Renaud, Guillaume, Jérôme, Margaux, les membres de l’association phi science... Bien évidemment, j’ai une très grosse pensée envers mes plus proches compagnons. Je tiens à remercier très chaleureusement Antoine Marion et Ilke Ugur, Daniel Bonhenry, Thibaud Etienne et Hugo Gattuso pour leur complicité, leur aide, leur soutient... mais surtout pour leur amitié! J’ai une pensée toute particulière pour Séverine Bonenberger qui m’a bien aidé pour toutes les démarches administratives mais surtout qui m’a soutenu moralement durant ces trois années. Je tiens aussi à remercier le professeur Vincent Robert pour son encadrement lors de mon stage de master ainsi que tout le personnel du laboratoire de chimie quantique de Strasbourg: Chantal, Sylvie, Paola, Christophe, Emmanuel, Étienne et Roberto L’accomplissement de cette thèse n’aurait jamais été possible sans le soutient infaillible de mes amis et de ma famille. Pour commencer, j’aimerais remercier de tout mon cœur la personne avec qui je partage ma vie depuis plusieurs années, Justine. Merci mon amour pour ton soutient sans faille dans tous les moments difficiles que j’ai passé durant ces trois années. Je tiens également à te remercier d’avoir concédé la poursuite de mon sport en dépit du peu de temps que nous passions ensemble. D’une manière générale, tout simplement merci d’avoir accepté de poursuivre ce bout de chemin, toi et moi, malgré l’éloignement. J’aimerais aussi remercier mes parents Sylvie et Claude, ainsi que Corinne et Yves. Merci Ma- man pour ta gentillesse, pour ton soutient dans les bons comme dans les mauvais moments et merci pour tout ce que tu as fait pour moi avant et pendant cette thèse. Merci Papa pour ta joie de vivre, ton optimisme et ton dynamisme que tu m’as transmis. J’aimerai également exprimer mes remer- ciements à toute ma famille et belle famille: Papy René, Mamie Françoise, Christine et Pierre, Sandrine et Philippe, Magali, Fabien, Timéo et Antonin, Philippe, Renate, Martine, Audrey et Jérémy, Bernard, Chantal, Olivier et sa famille, Monique et Mélanie, les parents, grands-parents ainsi que la sœur de Justine, Annick et Jean-Pierre, Clothilde, Simone, Jaques et Mamie Anna. v Je pense très fort à mon oncle Marcel et à ma grand-mère Yvonne qui ne sont plus là et dont la présence me manque beaucoup. Je tiens à remercier tous les membres du Vélo Club de Dorlisheim et tous mes partenaires d’entraînements. Pour tous les bons moments que nous avons passés ensemble, merci à mes trois supers cousins Mathias, Thibaut et Quentin. Je tiens également tout particulièrement à remercier ce dernier pour avoir concédé de jouer avec un coéquipier éloigné et très peu présent. Durant ces trois années j’ai partagé bon nombre de beaux moments au côté de mes amis notam- ment lors de sorties trails! Je souhaite vivement remercier : Mathilde, Jerem et le petit Gauthier, Joséphine et Thierry, Anthony et Julie, Franz et Julie. Je tiens également à remercier tout partic- ulièrement Alex et Léa, avec qui je me suis lié d’amitié durant cette thèse, pour leur accueil lors de mes derniers mois de thèse ainsi que pour tous les moments (sportifs ou autour d’un bon dîner) conviviaux passés à leur côté. Enfin je tenais à exprimer mes profonds regrets pour toutes les personnes que j’ai omis de citer dans ces quelques lignes. Donc à toutes celles et ceux que j’ai oublié j’aimerai tout de même dire : MERCI !!! vii Contents Acknowledgements/Remerciements iii Introduction 1 I The transferability of the extremely localized molecular orbitals 1 Linear Scaling Methods 9 1.1 Introduction ..................................... 11 1.2 The Divide and Conquer method and the Molecular Tailoring Approach . 14 1.3 The Fragment Molecular Orbital method .................... 23 1.4 The Additive Fuzzy Density Fragmentation approaches . 25 2 Localized Molecular Orbitals 31 2.1 Introduction ..................................... 33 2.2 Unitary Transformation Methods ......................... 34 2.3 Extremely Localized Molecular Orbitals: the Stoll technique . 37 2.4 Rotation ....................................... 42 3 Model molecule approximation and ELMOs transferability 49 3.1 Introduction ..................................... 51 3.2 Methods ....................................... 52 3.2.1 General strategy .............................. 52 3.2.2 Description of the target system ..................... 52 3.2.3 Model molecules approximation ..................... 53 3.2.4 Computational
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