Molecular Quantum Electrodynamics: Long-Range Intermolecular Interactions Book

Preface xi

1 Molecular Quantum Electrodynamics: Basic Theory 1

1.1 Background 1

1.2 Quantum Description of Matter 5

1.3 Electrodynamics and Maxwell Equations 8

1.4 Quantization of the Free Electromagnetic Field 14

1.5 Interacting Particle-Radiation Field System 26

1.6 Multipolar Lagrangian 30

1.7 Multipolar Hamiltonian 37

1.8 Canonical Transformation 42

1.9 Perturbation Theory Soluion 47

1.10 State Sequence Diagrams 55

2 Molecular Quantum Electrodynamics: Field Theoretic Treatment 60

2.1 Introduction 60

2.2 Nonrelativistic Quantum Field Theory 62

2.3 Quantum Canonical Transformation 71

2.4 Multipolar Maxwell Fields 77

2.5 Minimal-Coupling Maxwell Fields 83

2.6 Multipolar Maxwell Fields in the Vicinity of a Source 90

2.7 Higher Multipole Moment Maxwell Fields 98

2.8 Maxwell Fields of a Diamagnetic Source 101

2.9 Electromagnetic Energy Density 104

2.10 Poynting's Theorem and Poynting Vector 115

3 Intermolecular Forces 121

3.1 Concept of Intermolecular Potential 121

3.2 Short-Range Forces 125

3.3 Long-Range Forces 127

3.4 Electrostatic Interaction 128

3.5 Induction Forces 134

3.6 Dispersion Forces 136

4 Resonant Transfer of Energy 139

4.1 Introduction 139

4.2 Diagrammatic Perturbation Theory 142

4.3 State Sequence Diagram Representation 149

4.4 Energy Transfer Between Chiral Systems 152

4.5 Emitter-Absorber Model 157

4.6 Response Theory Calculation 161

4.7 Time-Dependent Energy Transfer and Causality 164

4.8 Proof of Causality of Energy Transfer to all Orders in Perturbation Theory 172

5 Retarded Dispersion Forces 175

5.1 Introduction 175

5.2 Casimir-Polder Potential: Perturbation Theory 178

5.3Near-Zone Potential: London Dispersion Energy 186

5.4 Far-Zone Dispersion Potential 189

5.5 State Sequence Diagrams for Dispersion Force 193

5.6 Dispersion Interaction Between One Ground an One Excited Molecule: Perturbation Theory 199

5.7 Response Theory Calculation of Dispersion Forces 207

5.8 Dispersion Potential via the Method of Induced Multipole Moments 216

5.9 Discriminatory Dispersion Interactions 222

5.9.1 Perturbation Theory 223

5.9.2 Response Theory 230

5.9.3 Induced Moment Approach 236

5.10 Interactions Involving Magnetically Susceptible Molecules 243

5.11 Measurements of Casimir Effect 251

6 Many-Body Forces 257

6.1 Introduction 257

6.2 Axilrod-Teller-Muto Dispersion Energy Shift 260

6.3 Retarded Triple-Dipole Dispersion Potential: Perturbation Theory 266

6.4 Triple-Dipole Dispersion Energy Shift via Craig-Power Hamiltonian 269

6.5 Triple-Dipole Dispersion Potential via Correlations of the Dressed Vacuum Field 277

6.6 N-Body Dispersion Potential 283

6.7 Four-Body Retarded Dispersion Potential 292

6.8 Three-Body Dispersion Interaction Involving One Excited Molecule 295

6.8.1 Time-Dependent Perturbation Theory 296

6.8.2 Coupling of Induced Dipoles 299

6.9 Mediation of Resonance Energy Transfer by a Third Body 304

7 Intermolecular Interactions in a Radiation Field 311

7.1 Introduction 311

7.2 Radiation-Induced Dispersion Force: Perturbation Theory 313

7.3 Dynamic Mechanism 315

7.4 Static Mechanism 321

7.5 Molecular and Pair Orientational Averaging 330

7.6 Polarization Analysis 332

7.6.1 Parallel Propagation 332

7.6.2 Perpendicular Propagation 334

7.7 Collapsed Graphs and Effective Interaction Hamiltonian 335

7.8 Radiation-Induced Intermolecular Interaction via the Method of Induced Moments 339

7.9 Discriminatory Intermolecular Interaction in a Radiation Field: Perturbation Theory 342

7.10 Radiation-Induced Chiral Discrimination: Induced Moment Method 348

7.10.1 Linearly Polarized Radiation 351

7.10.2 Circularly Polarized Radiation 352

7.11 Freely Tumbling Chiral Pair in the Presence of Circularly Polarized Light 353

7.12 Radiation-Induced Intermolecular Energy Shifts Involving Magnetic Dipole and Electric Quadrupole Polarizable Molecules 356

7.13 Higher Order Radiation-Induced Discriminatory Intermolecular Interaction 361

Appendix A Higher Multipole-Dependent Second-Order Maxwell Field Operators 370

Appendix B Rotational Averaging of Cartesian Tensors 378

References 381

Index 389