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First-Principles Simulations of the Interaction of Metal-Organic Molecules with a Surface and As Building Blocks for Nanodevices

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Universite´ de Strasbourg IPCMS: CNRS - UMR 7504 These` de Doctorat FIRST-PRINCIPLES SIMULATIONS OF THE INTERACTION OF METAL-ORGANIC MOLECULES WITH A SURFACE AND AS BUILDING BLOCKS FOR NANODEVICES par Burak Ozdamar¨ pr´esent´eeen vue d'obtenir le grade de Docteur de l'Universit´ede Strasbourg Sp´ecialit´e:Physique de la mati`erecondens´eeet des mat´eriaux Soutenue publiquement le 28/10/2016 `al'IPCMS devant le jury compos´ede: Prof. Dr. Roberto Marquardt UdS-LCQ Pr´esident Prof. Dr. J¨urg Hutter UZH-CMSZH Rapporteur Prof. Dr. Andres Saul AMU-CINaM Rapporteur Prof. Dr. Fabrizio Cleri UL1-IEMN Rapporteur Dr. S´ebastien Le Roux UdS-IPCMS Examinateur Prof. Dr. Mauro Boero UdS-IPCMS Directeur de th`ese Tired of lying in the sunshine staying home to watch the rain You are young and life is long and there is time to kill today And then one day you find ten years have got behind you No one told you when to run, you missed the starting gun. Roger Waters iii Abstract UNIVERSITE´ DE STRASBOURG Institut de Physique et Chimie des Mat´eriauxde Strasbourg Doctor of Philosophy FIRST-PRINCIPLES SIMULATIONS OF THE INTERACTION OF METAL-ORGANIC MOLECULES WITH A SURFACE AND AS BUILDING BLOCKS FOR NANODEVICES by Burak Ozdamar¨ The purpose of this study is to investigate the interaction of organometallic com- plexes with transition metals. This topic in question has a broad array of applica- tions in a number of domain; realization of nanojunctions for molecular nanoelec- tronics, biological imaging and nanocatalysis. Within this general framework, this PhD project aims to model the fundamental interactions of molecular building blocks at the atomic level in order to understand their role in the assembly and functionalization of nanostructures. The principal tool used in this study is first- principles simulation methods such as the Born-Oppenheimer and Car-Parrinello molecular dynamics. The first chapter presents an emphasis of the current de- velopments in the related field alongside of a retrospective on the historical de- velopments that leads today's knowledge. The second chapter presents the basic elements of the theory behind the methods that were used in the thesis, whose development has also been contributed during this research project. Lastly, the third chapter which is organized in three sub-chapters enumerates and describes the results of the various systems studied: i) Interaction of single Fe and Co atoms with ferrocene molecule which is also deposited on a Cu(111) slab in the perspective of possible molecular junctions. ii) Effects of water molecule traces on the ligand desorption process of precursor molecules, Fe and Co stearate, for functionalized Fe and Co oxide nanoparticle synthesis. iii) Investigation of the interaction of transition metals, Pt and Pd, with buckmin- sterfullerene (C60) molecule in the purpose of hydrogen storage and nanocatalysis applications. Majority of the work presented in this thesis has already been accepted in various journals for publication. B. Ozdamar,¨ C. Massobrio, M. Boero. Stability and Destabilization Pro- cesses in the Formation of Ferrocene-Based Metal{Organic Molecule{Metal Nano-Junctions. J. Phys. Chem. C, 120:1382, 2016. B. Ozdamar,¨ M. Boero, C. Massobrio, D. Felder-Flesch, S. Le Roux. Ex- ohedral M-C60 and M2-C60 (M = Pt, Pd) systems as tunable-gap building blocks for nanoarchitecture and nanocatalysis. J. Chem. Phys., 143:114308, 2015. M. Boero, A. Bouzid, S. Le Roux, B. Ozdamar,¨ and C. Massobrio. First- Principles Molecular Dynamics Methods: An Overview in Molecular Dynam- ics Simulations of Disordered Materials: From Network Glasses to Phase- Change Memory Alloys. C. Massobrio, J. Du, M. Bernasconi, and S. P. Salmon (Eds.), (pp. 33-55). Springer International Publishing, 2015. ISBN: 978-3-319-15674-3. Acknowledgements First and foremost, I would like to express my deepest gratitude to my supervisor Mauro Boero for conveying his vast knowledge in all aspects of computational physics and chemistry. This thesis would never have been complete, thorough and yet possible without his continuous and sincere assistance. For over three years of my PhD study, I have learned a lot from him, not only limited to science but also about social skills, if need be. I could never have thought a supervisor more intellectual, devoted, charitable and friendlier than him. I would like to thank Carlo Massobrio for his insightful contributions to my PhD study and his tips and tricks about acquiring the harmony in everyday life. I would also like to thank J¨urgHutter, Roberto Marquardt, Fabrizio Cleri, Andres Saul and S´ebastienLe Roux for accepting to attend as jury members and for their efficient and helpful corrections and suggestions. I am grateful to Assil Bouzid first for his friendship to help me adjust to Strasbourg in my early days and also for sparing his time to familiarize me with the functioning of CPMD. I would like to acknowledge Assil for his contributions to the calculations of stearate compounds. I am also thankful to Ziyad Chaker for his excellent friendship and for involving me with his fruitful (and generally challenging) scientific and philosophical discussions. I would like to thank Guido Ori and Emilie Delahaye with whom I share an office at different periods of my stay in IPCMS. I cannot pass without mentioning and thanking Hashim Jabbar, J´er^omeHurst, Adam Brandstetter-Kunc, Michal Studniarek, Ousmane Ly, Beata Taudul, Kevin Makles, Stanislav Makarchuk, Moussa Gueye and many others for their friendship. I would like to extend my deepest feelings to Burcu Onurlu for her emotional support and self-devotion when I was on the verge of losing my motivation. Last but not least, I am thankful to my parents for their endless support and encouragements. vii Contents Abstractv Acknowledgements vii Contents viii List of Figures xi List of Tables xix R´esum´e1 1 Introduction 25 1.1 State of the art............................. 26 2 Theoretical Background 41 2.1 Classical Molecular Dynamics..................... 42 2.2 Temperature Control.......................... 45 2.2.1 Velocity scaling......................... 46 2.2.2 Nos´e-Hoover Thermostat.................... 47 2.3 Tackling the Schr¨odingerEquation.................. 48 2.4 Density Functional Theory....................... 55 2.4.1 Definition of the Density.................... 55 2.4.2 Hohenberg-Kohn Theorems.................. 56 2.4.3 Kohn-Sham Equations..................... 60 2.4.4 Exchange and Correlation Functionals............ 63 2.4.4.1 Local Density Approximation (LDA)........ 64 2.4.4.2 Generalized Gradient Approximation (GGA)... 65 2.5 Solving the Kohn-Sham equations................... 67 2.5.1 Plane wave basis set...................... 67 ix Contents x 2.5.2 Pseudopotentials........................ 68 2.5.2.1 Non-linear core correction.............. 71 2.6 Born-Oppenheimer Molecular Dynamics............... 72 2.7 Car-Parrinello Molecular Dynamics.................. 74 2.8 van der Waals interactions....................... 77 2.9 Constrained Dynamics - Free energy calculation........... 78 2.9.1 Blue Moon sampling...................... 82 3 Results and Discussion 87 3.1 Single transition metal atom deposition on ferrocene molecule de- posited on Cu(111) substrate..................... 88 3.1.1 Ferrocene............................ 89 3.1.2 Computational Details..................... 93 3.1.3 Iron deposition......................... 94 3.1.4 Cobalt deposition........................ 97 3.2 Precursor molecules for the synthesis of Fe and Co oxide nanopar- ticles and related dissociation processes................ 105 3.2.1 Computational Details..................... 112 3.2.2 M-stearates in dry conditions (M=Fe, Co).......... 112 3.2.3 M-stearates with one H2O molecule.............. 119 3.2.4 M-stearates with two H2O molecule.............. 123 3.3 Exohedral M{C60 and M2{C60 (M = Pt, Pd) systems........ 133 3.3.1 Computational Details..................... 134 3.3.2 M-C60, M = Pt, Pd systems.................. 136 3.3.3 M2-C60, M= Pt, Pd systems.................. 143 4 General Conclusions 151 A 157 A.1 Average constraint force and free energy profile........... 157 Bibliography 160 List of Figures 1.1 Miniaturization of amplification devices starting from vacuum tubes to integrated circuits........................... 26 1.2 Evolution of the number of transistors on a single microprocessor die. 27 1.3 Schematic representation of a hypothetical molecular junction.... 28 1.4 Molecular rectifier proposed by Aviram and Ratner in 1974. TTF as a donor group, TCNQ as an acceptor group connected by a σ bridge................................... 29 1.5 The mechanism proposed by Aviram and Ratner, showing the elec- tron flow from the excited zwitterion state TTF+-σ-TCNQ− to the ground state TTF-σ-TCNQ. Adapted from [14]............ 30 1.6 A schematic representation of n-dode-canethiol (DT) and 4,4'-di(phenylene- ethynylene)-benzothioacetate (DPEBT) SAM on Auf111g. From [25]. Reprinted with permission from AAAS.............. 31 1.7 Molecular structures of sandwich bis(phthalocyaninato) rare earth double-decker complexes used as semiconductors of p-type OFET. From [31]. Reprinted with permission from Springer......... 32 1.8 Structure and electronic properties of PTCDA/Ag(111). (a) Bulk crystal structure (α-phase). (b) STS spectra of a PTCDA/Ag(111) monolayer. From [33]. Reprinted with permission from Nature Publishing Group............................. 33 1.9 An early drawing of the iron bis-cyclopentadienyl, namely ferrocene. This promising double-decker molecule
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