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Theoretical Study of Electronic Properties of Carbon Allotropes

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Theoretical Study of Electronic Properties of Carbon Allotropes Theoretical Study of Electronic Properties of Carbon Allotropes Theoretische Studien der elektronischen Eigenschaften von Kohlenstoff-Allotropen Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Pavlo O. Dral aus Moskau Als Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 4. Oktober 2013 Vorsitzender des Promotionsorgans: Prof. Dr. Johannes Barth Gutachter: Prof. Dr. Timothy Clark Prof. Dr. Rik R. Tykwinski Неньці Україні “There seems little danger that chemists will not always be able to imagine still larger systems meriting quantum chemical study” Christopher J. Cramer, “Essentials of Computational Chemistry: Theories and Models” Acknowledgements Acknowledgements First of all I am especially thankful to my supervisor Prof. Dr. Timothy Clark for his invaluable support during completing this project on both scientific and personal levels. Most of all I appreciate his remarkable ability to recognize my strong sides sometimes even better than I do myself. His confidence in me helped me to turn from the pure organic computational chemist to the developer of new quantum chemical software. His personal qualities such as his indefatigable ability always to be on the top and to lead the newest developments in so many different branches of science always encourage me on my own scientific way. I am very thankful to Prof. Dr. Andreas Hirsch for his excellent scientific cooperation and encouraging working in the field of novel carbon allotropes. Great thanks are dedicated also to Dr. Tatyana Shubina for her personal support before and during my study in Erlangen and for our fruitful scientific discussions. I am very thankful to many people from other groups for their excellent cooperation: Prof. Dr. Dirk Guldi, Vito Sgoba, Christian Ehli, Michael Sekita (Physical Chemistry I, Erlangen), Prof. Dr. Pietro Tagliatesta, Dr. Alina Ciammaichella (Rome), Prof. Dr. Rik Tykwinski, Dr. Milan Kivala, Dominik Prenzel (Chair I for Organic Chemistry, Erlangen), Prof. Dr. Marcus Halik (Institute of Polymer Materials, FAU), Prof. Dr. Andrey A. Fokin, Dr. Tatyana S. Zhuk, Pavel A. Gunchenko (Kyiv) and Prof. Dr. Peter R. Schreiner (Giessen), Prof. Dr. Nicolai Burzlaff, Nico Fritsch (Inorganic Chemistry, Erlangen), Prof. Dr. Peter Pulay (Fayetteville). I would like also to thank my colleagues in Computer-Chemie-Centrum (CCC), Interdisciplinary Center for Molecular Materials (ICMM) and Cluster of Excellence “Engineering of Advanced Materials” (EAM): Prof. Dr. Dirk Zahn, Prof. Dr. Bernd Meyer, Dr. Nico van Eikema Hommes (for his support with soft- and hardware problems and fruitful scientific discussions), Dr. Matthias Hennemann (for his support in development), Dr. Harald Lanig (for his support and help in translation), Dr. Pavel Rodzievich (a good man and friend), Dr. Christof Jäger (for discussions), Dr. Alexander Urban, Dr. Jakub Goclon, Dr. Sebastian Schenker (the first and very helpful roommate), Matthias Wildauer (for his sincere support, when I joint CCC), Ahmed El Kerdawy (for talks about life, science and morality), Marcus Pfau (for his help in German and English, and a good scientific collaboration), Thilo Bauer and Maximilian Kriebel (for discussions about I Acknowledgements electron transport), Christian Wick (for his help in German and collaboration), Ralf Kling, Heike Thomas, Theodor Milek, Philipp Ectors, Patrick Duchstein, Christina Ebensberger and Andy Krause. I owe many thanks to CCC secretaries: Isa, Nadine and Agnes. Graduate School Molecular Science (GSMS) and particularly Dr. Norbert Jux are greatly acknowledged for their help and many helpful joint meetings of the members of the GSMS in Kirchberg in Tirol, where we were able not only enrich our knowledge in chemistry, but more importantly get to know many people, make friends and make closer cooperation. I am also very thankful to Universität Bayern e.V. for a stipend within the Bavarian Elite Aid Program and for organizing excellent workshop. Support (financial, organizational via workshops facilitating communication with other groups etc.) from many organizations is also greatly appreciated. So, many theoretical studies presented in this thesis were supported by the Interdisciplinary Center for Molecular Materials and by the Deutsche Forschungsgesellschaft as part of the Excellence Cluster “Engineering of Advanced Materials”, SFB 953 “Synthetic Carbon Allotropes” and SFB 583, “Redox-Active Metal Complexes: Control of Reactivity via Molecular Architectures”, and by the "Solar Technologies Go Hybrid" initiative of the State of Bavaria. Computational resources provided by the Regional Computing Center Erlangen (RRZE), the Leibniz Rechenzentrum Munich and the High Performance Computing Center (HPCC) of National Technical University of Ukraine “KPI” are also acknowledged. The friendship of Igor Hytriuk and his family, Myhailo M. Gryp, Zlatko Brkljaca, Zoran Milicevic, Andrey Dolbichshenko and his family, Slava Bernat and Vova Lobaz are greatly valued too. I am very thankful to my fiancée Hanna for her deep understanding, love, support, patience, our talks and motivating me. At last but not least I am deeply obliged to my family, especially my grandmother, father and grandfather for their endless love, priceless support and encouragement during my whole life. II Zusammenfassung Zusammenfassung In der vorliegenden Doktorarbeit wird die theoretische Untersuchung der verschiedenen physikalisch-chemischen und vor allem elektronischen Eigenschaften von zahlreichen bereits entdeckten und noch zu synthetisierenden neuartigen Kohlenstoff-Allotropen, deren Modelverbindungen und Derivate dargestellt. Im letzten Jahrhundert wurde festgestellt, dass Kohlenstoff nicht nur das wichtigste chemische Element für die Existenz von Lebewesen ist, sondern auch zunehmend wichtiger für Elektronik und besonders in letzten Jahrzehnten für molekulare Nanoelektronik wird. Seine einzigartige Fähigkeit, unbegrenzte Mengen chemischer Verbindungen zu bilden, führt auch dazu, dass es auch scheinbar unendlich viel Allotropen mit sehr unterschiedlichen Eigenschaften hat. Die bis jetzt bekannten Kohlenstoff-Allotropen können vor allem nach Hybridisierung der Orbitalen ihrer Kohlenstoffatome klassifiziert werden: sp-Kohlenstoff kann zumindest theoretisch linearen azetylenischen Kohlenstoff bilden, sp2-Kohlenstoff – zahlreiche Allotropen mit graphenischen Oberflächen wie Graphit, Graphen, Kohlenstoffnanoröhre und Fullerene, sp3-Kohlenstoff – Diamant. Ihre Eigenschaften können weiter durch chemische Funktionalisierung gesteuert werden. Kleinere Modelverbindungen von sp-Kohlenstoff-Allotropen wie Polyine und Kumulene, sp2-Kohlenstoff wie polyzyklische aromatische Kohlenwasserstoffe, sp3-Kohlenstoff wie Diamantoide sind auch von großem Interesse, weil sie nicht nur oft einfacher theoretisch und experimental untersucht werden können, sondern auch selbst bemerkenswerte Eigenschaften haben. Außerdem sind die neuartige Kohlenstoff-Allotropen, die aus der Kombination von sp-, sp2- und sp3- hybridisierten Kohlenstoffen zusammengesetzt sind, wie sp-sp2-Graphdiin, sp-sp3-in-Diamant, sp2-sp3-Hexagonit und sp-sp2-sp3-Kohlenstoffe, die aus mit Kohlenstoffketten verbundenen Fullerenkugeln bestehen, denkbar und erweiterte Ausschnitte von einigen davon wurden bereits synthetisiert. Kohlenstoff-Allotropen, ihre Modelverbindungen und Derivaten finden immer häufiger Anwendung für Nanoelektronik und Elektronik, z. B. bei Bestandteilen von Transistoren, Sensoren und Speichergeräten, für Energiewandlung, wie es bei Bestandteilen von Solarzellen zu finden ist und für Energiespeicherung. Dementsprechend werden diese Substanzen in den letzten Jahren sehr intensiv experimental und theoretisch untersucht. Die Bedeutung der Studien von Kohlenstoff-Allotropen in Forschung und Entwicklung wurde mit den Nobelpreisen für Chemie im Jahre 1996 und für Physik im Jahre 2010 ausgezeichnet. Der III Zusammenfassung erste Nobelpreis wurde Robert F. Curl, Harold Kroto und Richard E. Smalley für die Entdeckung der Fullerene verliehen und der zweite wurde an Andre Geim und Konstantin Novoselov „für grundlegende Experimente mit dem zweidimensionalen Material Graphen“ vergeben. In dieser Arbeit werden Kohlenstoff-Allotropen und deren verwandten Verbindungen auf ihre wichtigen Eigenschaften für die Nanoelektronik bzw. Energiewandlung und -speicherung mit verschiedenen quantenchemischen Methoden wie ab initio und semiempirische sowie Dichtefunctionaltheorie (DFT) Verfahren untersucht. Semiempirische Konfigurations- wechselwirkungsmethoden (Configuration Interaction, CI) und DFT-Methoden werden verwendet, um die angeregten Zustände von molekularen Nanosystemen, die auf die oben genannten Verbindungen basiert sind, zu beschreiben. Detaillierte ab initio- und DFT-Studien der angeregten Zustände von relativ großen molekularen Nanosystemen mit weit über hundert Atomen sind mit der heutigen Entwicklung der Computertechnik zu rechenintensiv und deshalb sind semiempirische CI-Methoden (Configuration Interaction, CI) manchmal die einzige Wahl für solche Systeme. Demzufolge wurden neue semiempirische Unrestricted (HF) Natural Orbitals (UNO) – CI-Methoden entwickelt, die die anspruchsvolle Aufgabe der Auswahl der richtigen aktiven Orbitale für CI lösen. Darüber hinaus liefern UNO–CI-Methoden in der Regel höhere Genauigkeit als die konventionellen CI-Methoden und vergleichbare oder
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