pi-logic Veen, Maria Helena van der IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2006 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Veen, M. H. V. D. (2006). pi-logic [Groningen]: s.n. Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 01-02-2017
π-logic
Cover Based on Escher-type artwork provided by Dr. Joseph L. Teeters π-logic M.H. van der Veen Ph.D. Thesis University of Groningen, The Netherlands May 2006 The work described in this thesis was performed in the research group Chemistry of (Bio)Molecular Materials and Devices of the Stratingh Instituut, University of Groningen, The Netherlands. The work described in this thesis was financially supported by the MSC plus. MSC plus Ph.D. thesis series 2006-06 ISSN 1570-1530 ISBN 90-367-2518-6 (paperback version) ISBN 90-367-2519-4 (electronic version) Publisher Rijksuniversiteit Groningen, Groningen, The Netherlands Printing Grafisch bedrijf Ponsen & Looijen BV, Amsterdam, The Netherlands Copyright 2006, M. H. van der Veen All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without permission from the author.
RIJKSUNIVERSITEIT GRONINGEN π-logic Proefschrift ter verkrijging van het doctoraat in de Wiskunde en Natuurwetenschappen aan de Rijksuniversiteit Groningen op gezag van de Rector Magnificus, dr. F. Zwarts, in het openbaar te verdedigen op maandag 22 mei 2006 om 14.45 uur door Maria Helena van der Veen geboren op 13 januari 1978 te Hoogeveen
Promotor: Copromotor: Prof. dr. J. C. Hummelen Dr. H. T. Jonkman Beoordelingscommissie: Prof. dr. J. Knoester Dr. S. Roth Prof. dr. F. Wudl
Voor wie het leest Yesterday is history Today is a gift Tomorrow is mystery Mysteryland, 2005
Contents 1 Molecular Electronics 5 1.1 On the Way to Molecular Electronics 6 1.2 The Conjugated Double Bond 7 1.3 Topological Aspects of Quasi-particles 9 1.4 Valence Bond Theory and Molecular Orbital Theory 11 1.5 Molecular Scale Electronics 12 1.6 Challenges 18 1.7 Thesis objectives 19 1.8 References 21 2 On the Classification of n-terminal π-conjugated Systems 27 2.1 Introduction 28 2.2 Systematic Analysis of n-terminal Systems 30 2.3 Analysis of Fully Unsaturated n-terminal Systems: Fundamentals, Definitions, and Conventions 33 2.4 Classification of n-terminal π-conjugated Systems 37 2.5 Generalized Analysis of n-terminal Systems 44 2.6 Discussion 46 2.7 Conclusions 47 2.8 References and Notes 49 3 Topological Design of Omniconjugated Systems 53 3.1 Introduction 54 3.2 Wiring Molecular Wires 56 3.3 Design of Omniconjugated Models 58 3.3.1 Topological Design Program 58 3.3.2 Type B Omniconjugated Models 64 3.3.3 Quasi-omniconjugated Models 65 3.4 Topological Properties of Omniconjugated Models 67 3.5 Classification of n-terminal π-conjugated Systems: Extended 71 3.6 Real Chemical Examples of Omniconjugated Compounds 76 3.7 Conclusions 80 3.8 References and Notes 82
π-logic 4 Electronic structure of Omniconjugated compounds 87 4.1 Introduction 88 4.2 Quantum-Chemical approach 89 4.3 Frontier Orbital Delocalization 91 4.4 Frontier Orbital Localization 94 4.5 Discussion and Conclusions 96 4.6 References 98 5 Group Theoretical Aspects: A Quest for Control and Understanding 101 5.1 Introduction 102 5.2 The Symmetry Properties of n-terminal Systems 104 5.3 The Construction of a Group based on π-topology 109 5.4 The Basis for Understanding π-topological Properties 113 5.5 Mathematical Basis for the Design of π-logic 119 5.6 Discussion 124 5.7 Conclusions 125 5.8 References and Notes 127 6 π-logic: Topologies for Boolean Functions inside Single π-conjugated Molecules 129 6.1 Introduction 130 6.2 Logic Gates from Two Switches Based on π-conjugation 132 6.3 All Boolean Functions inside Compact π-logic Gates 136 6.4 Increasing the Complexity: Bifunctional Logic Elements 141 6.5 On the Built-in Logic of n-terminal π-conjugated Systems 143 6.6 Discussion and Conclusions 148 6.7 References and Notes 151 Appendix A 5-Terminal Archetype Series 155 Appendix B G 5A Group Multiplication Table 156 Appendix C 6-Terminal Archetype Series 157 Appendix D Truth Tables of Boolean Functions 158 2
Contents Summary 159 Samenvatting 161 Dankwoord 167 3