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Molecular Electronics
An Introduction to Theory and Experiment

World Scientific Series in Nanoscience and Nanotechnology

Series Editor: Mark Reed (Yale University)

Vol. 1 Molecular Electronics: An Introduciton to Theory and Experiment Juan Carlos Cuevas (Universidad Autnoma de Madrid, Spain) & Elke Scheer (Universitt Konstanz, Germany)

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Volume

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Molecular Electronics
An Introduction to Theory and Experiment

World Scientic Series in Nanoscience and Nanotechnology

Universidad Autnoma de Madrid, Spain Universitt Konstanz, Germany

Juan Carlos Cuevas Elke Scheer

World Scientific
NEW JERSEY

LONDON

SINGAPORE

BEIJING

SHANGHAI

HONG KONG

TA I P E I

CHENNAI

Published by World Scientific Publishing Co. Pte. Ltd. 5 Toh Tuck Link, Singapore 596224 USA office: 27 Warren Street, Suite 401-402, Hackensack, NJ 07601 UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE

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British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library.

World Scientific Series in Nanoscience and Nanotechnology Vol. 1 MOLECULAR ELECTRONICS An Introduction to Theory and Experiment Copyright 2010 by World Scientific Publishing Co. Pte. Ltd. All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the Publisher.

For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher.

ISBN-13 978-981-4282-58-1 ISBN-10 981-4282-58-8

Printed in Singapore.

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To our families

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Preface

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The trend in the miniaturization of electronic devices has naturally led to the question of whether or not it is possible to use single molecules as active elements in nanocircuits for a variety of applications. The recent developments in nanofabrication techniques have made possible the old dream of contacting individual molecules and exploring their electronic transport properties. Moreover, it has been shown that molecules can indeed mimic the behavior of some of todays microelectronic components, and even strategies to interconnect molecular devices have already been developed. These achievements have given rise to what is nowadays known as Molecular Electronics. There are still many problems and challenges to be faced to make this novel electronics a viable technology, but the exploration of molecular-scale circuits has already led to the discovery of many fundamental eects. In this sense, molecular electronics has become a new interdisciplinary eld of science, in which knowledge from traditional disciplines like physics, chemistry, engineering and biology is combined to understand the electrical and thermal conduction at the molecular scale. This book provides a comprehensive overview of the rapidly developing eld of molecular electronics. It focuses on our present understanding of the electrical conduction in single-molecule circuits and presents a thorough introduction to the experimental techniques and the theoretical concepts. To be precise, our goal in this monograph is two-fold. On the one hand, we want to provide a true textbook for advanced undergraduate and graduate students both in physics and chemistry who are interested in the eld of molecular electronics or nanoelectronics in general. Our idea is to take a student with a good background in quantum mechanics all the way to be able to follow the specialized literature in molecular electronics or to start working in this eld. On the other hand, we also want provide a
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thorough review of the recent activities in molecular electronics from which newcomers and specialists in the eld can benet. Bearing these goals in mind, this book has been written in a selfcontained and unied way. It contains four parts that can be read independently. In the rst two ones we review the basic experimental techniques and the main theoretical concepts concerning the electronic transport in atomic-scale junctions. These two parts are meant to be textbook material for an advanced course in molecular electronics. In particular, we have included a collection of exercises at the end of most chapters, which in many cases are motivated by recent experiments in the eld. On the other hand, Part 3 contains two chapters in which we describe at an introductory level the physics of metallic atomic-size contacts and we also point out some of the remaining challenges and open problems in this context. Finally, Part 4 is devoted to the electrical and thermal transport in molecular circuits, with special emphasis on single-molecule junctions. Here, we do not only review the recent activities in the eld of molecular electronics, but we also introduce the addressed topics at a basic level. In this sense, we have often included unpublished material and additional exercises to help the reader to gain a deeper insight into the fundamental concepts involved in the eld of molecular electronics.1 We have tried to cover in this monograph as many aspects of molecular electronics as possible, but obviously the selection is limited for space reasons and it reects unavoidably our own research interests. We also want to apologize with those authors that feel that their contribution was not properly highlighted in the review part of this monograph, but it is by now impossible to include all the huge amount of work done in this eld. Finally, we just hope to have achieved, at least partially, the goal that truly motivated the writing of this book, namely the sincere will to provide a useful book for the new generation of researchers that should consolidate molecular electronics as a solid pillar of the emerging nanoscience.

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1 See

section 1.3 for a more detailed description of the structure and scope of the book.

Acknowledgments

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It would not have been possible to write the book without the help of many coworkers and colleagues. First of all, we want to thank Edith Goldberg for encouraging one of us (JCC) to give a postgraduate course on molecular electronics in the fall of 2008 in Santa Fe (Argentina). The excellent students who attended that course demonstrated that, after a 50-hours course and without any previous knowledge about this eld, one can master the basic concepts and techniques that now form the body of this monograph. This fact provided the nal boost that we needed to collect all our notes and turn them into this book. Similarly, for the experimental point of view of this book, the students in the graduate course at Konstanz served as test candidates. Some of them even got contaminated by this exciting eld and went on asking questions what nally resulted in contributions to this book. Very valuable input came from my colleague Artur Erbe who was the real expert in molecular electronics in our Department until he left to Dresden. We also want to express our gratitude to Alvaro Mart n Rodero, who not only introduced one of us (JCC) to the exciting eld of nanoelectronics, but also contributed decisively to this manuscript with his personal notes, which are the basis of several chapters of the theoretical background. The same holds for Hilbert von L ohneysen and Cristi an Urbina who sent the other one of us (ES) to perform experiments with nanoelectronic circuits. We would especially like to thank our coworkers Fabian Pauly, Janne K. Viljas, Michael H afner, S oren Wohlthat, Stefan Bilan, Linda A. Zotti, C ecile Bacca, Stefan B achle, Tobias B ohler, Uta Eberlein, Stefan Egle, Daniel Guhr, Ning Kang, Thomas Kirchner, Christian Kreuter, Shou-Peng Liu, Youngsang Kim, Hans-Fridtjof Pernau, Olivier Schecker, Christian Schirm, Dima Sysoiev, Simon Verleger, and Reimar Waitz. They have contributed
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Molecular Electronics: An Introduction to Theory and Experiment

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to this manuscript with many results, special gures and very important suggestions and critical comments about the text. Thanks go also sincerely to our colleagues who have read dierent parts of the manuscript and have provided helpful comments: Douglas Natelson, Abraham Nitzan, Wilson Ho, Latha Venkataraman, and Arunava Majumdar. This monograph reects our view of this eld, which has emerged thanks to the collaboration and exchange of ideas with many colleagues over the years. So in this respect, we want to thank Alfredo Levy Yeyati, Gerd Sch on, Jan Heurich, Wolfgang Wenzel, Jan M. van Ruitenbeek, Nicol as Agra t, Gabino Rubio, Roel Smit, Oren Tal, Markus Dreher, Peter Nielaba, Christoph S urgers, Maya Lukas, Christoph Strunk, Sophie Gu eron, Richard Berndt, Paul Leiderer, Wolfgang Belzig, Marcel Mayor, Thomas Huhn, Andreas Marx, Ulrich Steiner, and Ulrich Groth. We also want acknowledge the contribution of all the authors who have kindly granted us the permission to reprint their work in this monograph. Finally, I (JCC) want to thank my parents and brothers for being always by my side. I also want to thank Ana for being so patient and share my time with this book for too many nights and weekends. ES thanks her family for continuous support and reminding me steadily of what is really important in life.

Contents

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Preface Acknowledgments

vii ix

Brief history of the eld and experimental techniques

1. The birth of molecular electronics 1.1 1.2 1.3 Why molecular electronics? . . . . . . . . . . . . . . . . . A brief history of molecular electronics . . . . . . . . . . . Scope and structure of the book . . . . . . . . . . . . . .

1
3 5 6 14 19 19 19 21 22 23 24 31 35 37 38 43

2. Fabrication of metallic atomic-size contacts 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . Techniques involving the scanning electron microscope (STM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods using atomic force microscopes (AFM) . . . . . Contacts between macroscopic wires . . . . . . . . . . . . Transmission electron microscope . . . . . . . . . . . . . . Mechanically controllable break-junctions (MCBJ) . . . . Electromigration technique . . . . . . . . . . . . . . . . . Electrochemical methods . . . . . . . . . . . . . . . . . . . Recent developments . . . . . . . . . . . . . . . . . . . . . Electronic transport measurements . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .
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3. Contacting single molecules: Experimental techniques 3.1 3.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . Molecules for molecular electronics . . . . . . . . . . . . . 3.2.1 Hydrocarbons . . . . . . . . . . . . . . . . . . . . 3.2.2 All carbon materials . . . . . . . . . . . . . . . . . 3.2.3 DNA and DNA derivatives . . . . . . . . . . . . . 3.2.4 Metal-molecule contacts: anchoring groups . . . . 3.2.5 Conclusions: molecular functionalities . . . . . . . Deposition of molecules . . . . . . . . . . . . . . . . . . . Contacting single molecules . . . . . . . . . . . . . . . . . 3.4.1 Electromigration technique . . . . . . . . . . . . . 3.4.2 Molecular contacts using the transmission electron microscope . . . . . . . . . . . . . . . . . . . . . . 3.4.3 Gold nanoparticle dumbbells . . . . . . . . . . . . 3.4.4 Scanning probe techniques . . . . . . . . . . . . . 3.4.5 Mechanically controllable break-junctions (MCBJs) Contacting molecular ensembles . . . . . . . . . . . . . . . 3.5.1 Nanopores . . . . . . . . . . . . . . . . . . . . . . 3.5.2 Shadow masks . . . . . . . . . . . . . . . . . . . . 3.5.3 Conductive polymer electrodes . . . . . . . . . . . 3.5.4 Microtransfer printing . . . . . . . . . . . . . . . . 3.5.5 Gold nanoparticle arrays . . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

45 45 46 47 50 51 52 52 53 55 56 58 59 60 64 66 66 68 69 70 71 73

3.3 3.4
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3.5

3.6

Theoretical background
4. The scattering approach to phase-coherent transport in nanocontacts 4.1 4.2 4.3 4.4 4.5 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . From mesoscopic conductors to atomic-scale junctions . . Conductance is transmission: Heuristic derivation of the Landauer formula . . . . . . . . . . . . . . . . . . . . . . . Penetration of a potential barrier: Tunnel eect . . . . . . The scattering matrix . . . . . . . . . . . . . . . . . . . . 4.5.1 Denition and properties of the scattering matrix 4.5.2 Combining scattering matrices . . . . . . . . . . . Multichannel Landauer formula . . . . . . . . . . . . . . .

75
77 77 79 81 83 88 88 91 92

4.6

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4.7 4.8 4.9 4.10

Conductance quantization in 2DEG: Landauer formula at work . . . . . . . . . . . . . . . . . Shot noise . . . . . . . . . . . . . . . . . . . . . . . . . Thermal transport and thermoelectric phenomena . . Limitations of the scattering approach . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . .

4.6.1

. . . . .

. 97 . 99 . 104 . 106 . 107

5. Introduction to Greens function techniques for systems in equilibrium

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111 . . . . . . . . . . . 112 113 118 118 122 124 128 131 134 136 139 143 144 146 148 149 151 152 157 158 162 167 170 171 173 175

5.1 5.2 5.3

5.4

5.5

The Schr odinger and Heisenberg pictures . . . . . . . . Greens functions of a noninteracting electron system . . Application to tight-binding Hamiltonians . . . . . . . . 5.3.1 Example 1: A hydrogen molecule . . . . . . . . 5.3.2 Example 2: Semi-innite linear chain . . . . . . 5.3.3 Example 3: A single level coupled to electrodes Greens functions in time domain . . . . . . . . . . . . . 5.4.1 The Lehmann representation . . . . . . . . . . . 5.4.2 Relation to observables . . . . . . . . . . . . . . 5.4.3 Equation of motion method . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . .

6. Greens functions and Feynman diagrams 6.1 6.2 6.3 6.4 6.5 The interaction picture . . . . . . . . . . . . . . . . . . . . The time-evolution operator . . . . . . . . . . . . . . . . . Perturbative expansion of causal Greens functions . . . . Wicks theorem . . . . . . . . . . . . . . . . . . . . . . . . Feynman diagrams . . . . . . . . . . . . . . . . . . . . . . 6.5.1 Feynman diagrams for the electron-electron interaction . . . . . . . . . . . . . . . . . . . . . . . . . 6.5.2 Feynman diagrams for an external potential . . . Feynman diagrams in energy space . . . . . . . . . . . . . Electronic self-energy and Dysons equation . . . . . . . . Self-consistent diagrammatic theory: The Hartree-Fock approximation . . . . . . . . . . . . . . . . . . . . . . . . The Anderson model and the Kondo eect . . . . . . . . . 6.9.1 Friedel sum rule . . . . . . . . . . . . . . . . . . . 6.9.2 Perturbative analysis . . . . . . . . . . . . . . . . Final remarks . . . . . . . . . . . . . . . . . . . . . . . . .

6.6 6.7 6.8 6.9

6.10

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Molecular Electronics: An Introduction to Theory and Experiment

6.11

Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . 176 179

7. Nonequilibrium Greens functions formalism 7.1 7.2 7.3

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7.4

7.5

The Keldysh formalism . . . . . . . . . . . . . . . . . . . 180 Diagrammatic expansion in the Keldysh formalism . . . . 184 Basic relations and equations in the Keldysh formalism . 186 7.3.1 Relations between the Greens functions . . . . . 186 7.3.2 The triangular representation . . . . . . . . . . . 187 7.3.3 Unperturbed Keldysh-Greens functions . . . . . . 189 7.3.4 Some comments on the notation . . . . . . . . . . 191 Application of Keldysh formalism to simple transport problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191 7.4.1 Electrical current through a metallic atomic contact 193 7.4.2 Shot noise in an atomic contact . . . . . . . . . . 199 7.4.3 Current through a resonant level . . . . . . . . . . 200 Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

8. Formulas of the electrical current: Exploiting the Keldysh formalism 8.1 Elastic current: Microscopic derivation of the Landauer formula . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.1.1 An example: back to the resonant tunneling model 8.1.2 Nonorthogonal basis sets . . . . . . . . . . . . . . 8.1.3 Spin-dependent elastic transport . . . . . . . . . . Current through an interacting atomic-scale junction . . . 8.2.1 Electron-phonon interaction in the resonant tunneling model . . . . . . . . . . . . . . . . . . . . . 8.2.2 The Meir-Wingreen formula . . . . . . . . . . . . Time-dependent transport in nanoscale junctions . . . . . 8.3.1 Photon-assisted resonant tunneling . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

205 205 211 212 213 215 217 222 224 231 233 237

8.2

8.3 8.4

9. Electronic structure I: Tight-binding approach 9.1 9.2 9.3 9.4 Basics of the tight-binding approach . . . The extended H uckel method . . . . . . . Matrix elements in solid state approaches 9.3.1 Two-center matrix elements . . . Slater-Koster two-center approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

237 241 242 244 246

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9.5

9.6 9.7

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9.8

Some illustrative examples . . . . . . . . . . . . . . . . . . 9.5.1 Example 1: A benzene molecule . . . . . . . . . . 9.5.2 Example 2: Energy bands in line, square and cubic Bravais lattices . . . . . . . . . . . . . . . . . . . . 9.5.3 Example 3: Energy bands of graphene . . . . . . The NRL tight-binding method . . . . . . . . . . . . . . . The tight-binding approach in molecular electronics . . . 9.7.1 Some comments on the practical implementation of the tight-binding approach . . . . . . . . . . . . 9.7.2 Tight-binding simulations of atomic-scale transport junctions . . . . . . . . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

247 248 250 252 253 257 258 259 260 263 264 264 265 266 268 269 271 273 273 275 277 277 278 280 282 284 285 291 292

10. Electronic structure II: Density functional theory 10.1 Elementary quantum mechanics . . . . . . . . . . . . . . . 10.1.1 The Schr odinger equation . . . . . . . . . . . . . . 10.1.2 The variational principle for the ground state . . 10.1.3 The Hartree-Fock approximation . . . . . . . . . . Early density functional theories . . . . . . . . . . . . . . The Hohenberg-Kohn theorems . . . . . . . . . . . . . . . The Kohn-Sham approach . . . . . . . . . . . . . . . . . . The exchange-correlation functionals . . . . . . . . . . . . 10.5.1 LDA approximation . . . . . . . . . . . . . . . . . 10.5.2 The generalized gradient approximation . . . . . . 10.5.3 Hybrid functionals . . . . . . . . . . . . . . . . . . The basic machinery of DFT . . . . . . . . . . . . . . . . 10.6.1 The LCAO Ansatz in the Kohn-Sham equations . 10.6.2 Basis sets . . . . . . . . . . . . . . . . . . . . . . . DFT performance . . . . . . . . . . . . . . . . . . . . . . DFT in molecular electronics . . . . . . . . . . . . . . . . 10.8.1 Combining DFT with NEGF techniques . . . . . 10.8.2 Pluses and minuses of DFT-NEGF-based methods Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

10.2 10.3 10.4 10.5

10.6

10.7 10.8

10.9

Metallic atomic-size contacts

11. The conductance of a single atom 11.1

293
295

Landauer approach to conductance: brief reminder . . . . 296

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Molecular Electronics: An Introduction to Theory and Experiment

11.2 11.3 11.4 11.5

Conductance of atomic-scale contacts . . . . . . . . . . . Conductance histograms . . . . . . . . . . . . . . . . . . . Determining the conduction channels . . . . . . . . . . . . The chemical nature of the conduction channels of oneatom contacts . . . . . . . . . . . . . . . . . . . . . . . . . 11.6 Some further issues . . . . . . . . . . . . . . . . . . . . . . 11.7 Conductance uctuations . . . . . . . . . . . . . . . . . . 11.8 Atomic chains: Parity oscillations in the conductance . . . 11.9 Concluding remarks . . . . . . . . . . . . . . . . . . . . . 11.10 Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .
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297 300 304 308 316 319 322 331 332

12. Spin-dependent transport in ferromagnetic atomic contacts 12.1 12.2 12.3 12.4 Conductance of ferromagnetic atomic contacts . . . Magnetoresistance of ferromagnetic atomic contacts Anisotropic magnetoresistance in atomic contacts . . Concluding remarks and open problems . . . . . . . . . . . . . . . . . . .

335 336 343 347 353

Transport through molecular junctions

13. Coherent transport through molecular junctions I: Basic concepts 13.1 13.2 Identifying the transport mechanism in single-molecule junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . Some lessons from the resonant tunneling model . . . . . 13.2.1 Shape of the I-V curves . . . . . . . . . . . . . . . 13.2.2 Molecular contacts as tunnel junctions . . . . . . 13.2.3 Temperature dependence of the current . . . . . . 13.2.4 Symmetry of the I-V curves . . . . . . . . . . . . 13.2.5 The resonant tunneling model at work . . . . . . A two-level model . . . . . . . . . . . . . . . . . . . . . . Length dependence of the conductance . . . . . . . . . . . Role of conjugation in -electron systems . . . . . . . . . Fano resonances . . . . . . . . . . . . . . . . . . . . . . . Negative dierential resistance . . . . . . . . . . . . . . . Final remarks . . . . . . . . . . . . . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

355
357 359 364 366 368 369 371 373 374 377 381 382 385 388 389

13.3 13.4 13.5 13.6 13.7 13.8 13.9

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14. Coherent transport through molecular junctions II: Test-bed molecules 14.1 Coherent transport through some test-bed molecules . . . 14.1.1 Benzenedithiol: how everything started . . . . . . 14.1.2 Conductance of alkanedithiol molecular junctions: A reference system . . . . . . . . . . . . . . . . . 14.1.3 The smallest molecular junction: Hydrogen bridges . . . . . . . . . . . . . . . . . . . . . . . . 14.1.4 Highly conductive benzene junctions . . . . . . . . Metal-molecule contact: The role of anchoring groups . . Tuning chemically the conductance: The role of side-groups . . . . . . . . . . . . . . . . . . . . . . . . . . Controlled STM-based single-molecule experiments . . . . Conclusions and open problems . . . . . . . . . . . . . . . Coulomb blockade and

391 392 392 395 401 405 408 412 416 420

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14.2 14.3 14.4 14.5

15. Single-molecule transistors: Kondo physics 15.1 15.2 15.3 15.4

423 423 425 429 432 432 435 436 439 445 447 449 451 451 453 456 468 473

15.5

15.6

15.7 15.8

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . Charging eects in transport through nanoscale devices . Single-molecule three-terminal devices . . . . . . . . . . . Coulomb blockade theory: Constant interaction model . . 15.4.1 Formulation of the problem . . . . . . . . . . . . . 15.4.2 Periodicity of the Coulomb blockade oscillations . 15.4.3 Qualitative discussion of the transport characteristics . . . . . . . . . . . . . . . . . . . . 15.4.4 Amplitudes and line shapes: Rate equations . . . Towards a theory of Coulomb blockade in molecular transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15.5.1 Many-body master equations . . . . . . . . . . . . 15.5.2 A simple example: The Anderson model . . . . . Intermediate coupling: Cotunneling and Kondo eect . . 15.6.1 Elastic and inelastic cotunneling . . . . . . . . . . 15.6.2 Kondo eect . . . . . . . . . . . . . . . . . . . . . Single-molecule transistors: Experimental results . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

16. Vibrationally-induced inelastic current I: Experiment 16.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 473

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Molecular Electronics: An Introduction to Theory and Experiment

16.2 16.3 16.4 16.5 16.6

Inelastic electron tunneling spectroscopy (IETS) . . . . Highly conductive junctions: Point-contact spectroscopy (PCS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . Crossover between PCS and IETS . . . . . . . . . . . . Resonant inelastic electron tunneling spectroscopy (RIETS) . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary of vibrational signatures . . . . . . . . . . . .

. 475 . 483 . 490 . 493 . 499 501

17. Vibrationally-induced inelastic current II: Theory 17.1

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17.2 17.3

17.4 17.5

Weak electron-phonon coupling regime . . . . . . . . . 17.1.1 Single-phonon model . . . . . . . . . . . . . . 17.1.2 Ab initio description of inelastic currents . . . Intermediate electron-phonon coupling regime . . . . . Strong electron-phonon coupling regime . . . . . . . . 17.3.1 Coulomb blockade regime . . . . . . . . . . . . 17.3.2 Interplay of Kondo physics and vibronic eects Concluding remarks and open problems . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . .

. . . . . . . . .

501 502 512 520 524 524 532 534 535

18. The hopping regime and transport through DNA molecules 18.1 18.2 18.3 18.4 Signatures of the hopping regime . . . . . . . . . . . . . . Hopping transport in molecular junctions: Experimental examples . . . . . . . . . . . . . . . . . . . . . . . . . . . DNA-based molecular junctions . . . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

537 538 541 546 552

19. Beyond electrical conductance: Shot noise and thermal transport 19.1 19.2 Shot noise in atomic and molecular junctions Heating and heat conduction . . . . . . . . . 19.2.1 General considerations . . . . . . . . 19.2.2 Thermal conductance . . . . . . . . . 19.2.3 Heating and junction temperature . . Thermoelectricity in molecular junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

553 554 560 561 562 565 569

19.3

20. Optical properties of current-carrying molecular junctions

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Contents

xix

20.1 20.2 20.3

20.4 20.5
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20.6 20.7 20.8 20.9

Surface-enhanced Raman spectroscopy of molecular junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . Transport mechanisms in irradiated molecular junctions . Theory of photon-assisted tunneling . . . . . . . . . . . . 20.3.1 Basic theory . . . . . . . . . . . . . . . . . . . . . 20.3.2 Theory of PAT in atomic contacts . . . . . . . . . 20.3.3 Theory of PAT in molecular junctions . . . . . . . Experiments on radiation-induced transport in atomic and molecular junctions . . . . . . . . . . . . . . . . . . . . . . Resonant current amplication and other transport phenomena in ac driven molecular junctions . . . . . . . . . . Fluorescence from current-carrying molecular junctions . Molecular optoelectronic devices . . . . . . . . . . . . . . Final remarks . . . . . . . . . . . . . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

580 583 585 586 590 592 594 601 604 608 613 614 617

21. What is missing in this book?

Appendixes
Appendix A Second Quantization A.1 Harmonic oscillator and phonons . . . . . . . . . . . . . . A.1.1 Review of simple harmonic oscillator quantization A.1.2 1D harmonic chain . . . . . . . . . . . . . . . . . Second quantization for fermions . . . . . . . . . . . . . . A.2.1 Many-body wave function in second quantization A.2.2 Creation and annihilation operators . . . . . . . . A.2.3 Operators in second quantization . . . . . . . . . A.2.4 Some special Hamiltonians . . . . . . . . . . . . . Second quantization for bosons . . . . . . . . . . . . . . . Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . .

621
623 624 624 626 628 628 630 632 634 637 638 639 699

A.2

A.3 A.4

Bibliography Index