Table of Contents
Preface vii
1 Electronic Structure of Metal-Molecule Interfaces H. Petek M. Feng J. Zhao 1
1.1 Introduction 1
1.2 Image Charge Interaction at Metal Surfaces 4
1.3 Hybrid NFE Band Formation at Metal-Organic Interface 8
1.3.1 C6F6 Quantum Well State 8
1.3.2 PTCDA Metal-Organic Interface State 12
1.4 Metal-Like Hybridization of Superatom States 14
1.4.1 Superatom States of C60 16
1.4.2 NFE Band Formation by Superatom States of C60 17
1.5 Conclusions 20
References 21
2 Inelastic Tunneling Current-Driven Motions of Single Adsorbates H. Ueba S. G. Tikhodeev B. N. J. Persson 26
2.1 Introduction 26
2.2 Theory of STM-IETS 35
2.2.1 Adsorbate-Induced Resonance Model of IETS 35
2.2.2 NEGF Theory of IETS and Vibrational Heating 41
2.2.3 Competition Between Elastic and Inelastic Current 45
2.3 Adsorbate Motions Induced by Vibrational Excitation with STM 50
2.3.1 Vibrational Ladder Climbing-Vibrational Heating 50
2.3.2 Physical Meaning of γjet 52
2.3.3 Numerical Examples of Inelastic Tunneling Current 55
2.4 Coherent Ladder Climbing 59
2.4.1 Coherent versus Incoherent Process 61
2.5 Single-Electron Process via Anharmonic Mode Coupling 63
2.5.1 Two-Electron Processes via Mode Coupling 74
2.6 Action Spectroscopy 78
2.7 Perspective Remarks 83
References 84
3 DFT-NEGF Approach to Current-Induced Forces, Vibrational Signals, and Heating in Nanoconductors M. Brandbyge T. Frederiksen M. Paulsson 90
3.1 Introduction 90
3.2 DFT-NEGF 92
3.3 Elastic Transport Channels: Eigenchannels 96
3.4 Inelastic Transport with DFT-NEGF 99
3.4.1 Electron-Phonon Interactions: The Self-Consistent Born Approximation 101
3.4.2 Electron-Phonon Interactions: The Lowest-Order Expansion 103
3.4.3 Example: Atomic Gold Wire 105
3.4.4 Example: Hydrocarbon Molecules Between Gold Contacts 107
3.5 IETS Propensity Rules 108
3.6 Heating of Vibrations by Current 111
3.7 Conclusions and Outlook 117
References 117
4 Current-Induced Local Heating in Molecular Junctions Z. F. Huang N. J. Tao 123
4.1 Current-Induced Instability 123
4.1.1 Local Heating in Single-Molecule Junctions 124
4.1.2 Theory of Current-Induced Local Heating 125
4.1.3 Comparison of Molecular Junctions with Metallic Point Contacts 127
4.2 Evaluation of Local Temperature in Molecular Junctions 128
4.2.1 Thermodynamic Theory of Chemical Bond Breakdown 129
4.2.2 Repeated Creation of Single-Molecule Junctions 130
4.3 Local Temperature in Single-Alkanedithiol Junctions 131
4.3.1 Thermodynamic Dissociation 132
4.3.2 Bias Dependence of Single-Alkanedithiol Conductance 133
4.3.3 Bias and Molecular Length Dependence of Local Temperature 134
4.4 Conclusion and Perspective 135
References 136
5 Current-Induced Heating and Heat Dissipation Mechanisms in Single C60 Molecular Junctions G. Schulze K. J. Franke J. I. Pascual 139
5.1 Experimental Methods 141
5.2 Experimental Procedure 144
5.3 Results 145
5.4 Heat Dissipation from the Molecular Junction 148
5.4.1 Mechanism of Heat Dissipation 149
5.5 Heat Generation at the Molecular Junction 152
5.6 Summary 154
References 154
6 Electronic Control of Single-Molecule Nanomachines A. J. Mayne D. Riedel G. Comtet G. Dujardin 156
6.1 Introduction and Historical Background 156
6.2 Electronic Excitation 157
6.2.1 Electron Attachment 157
6.2.2 Electronic Transition 166
6.2.3 Electron-Hole Pair Attachment 166
6.3 Manipulating Molecules 168
6.4 Manipulation of a Bistable and Quadristable Molecule: Biphenyl on Si(100) 172
6.5 Other Avenues 176
6.5.1 Molecules on Passivated or Insulating Surfaces 179
6.5.2 Molecules on Wide-Band-Gap Semiconductors 183
6.5.3 Laser-STM 185
6.6 Conclusions 188
References 189
7 Current-Driven Desorption at the Organic Molecule-Semiconductor Interface: Cyclopentene on Si(100) N. L. Yoder R. Jorn C.-C. Kaun T. Seideman M. C. Hersam 196
7.1 Introduction and Background 196
7.2 Methods 198
7.2.1 Experimental Procedures 198
7.2.2 Numerical Procedures 198
7.3 System 201
7.4 Experimental Results 202
7.5 Numerical Results 206
7.5.1 Physical and Electronic Structure 207
7.5.2 Electronic Transport Calculations 210
7.5.3 Reaction Dynamics Studies 212
7.6 Relevance to Other Systems 214
7.7 Conclusion 215
References 217
Index 220
