Optical properties of metal clusters

Cover......Page 1
Title page......Page 3
Copyright page......Page 4
Preface......Page 5
Table of Contents......Page 9
List of Symbols and Abbreviations......Page 15
List of Tables......Page 19
1. Introduction......Page 21
2. Theoretical Considerations......Page 33
a) Free Electron Optical Response......Page 34
b) Interband Transitions and Core Effects in Realistic Metals......Page 36
c) Fundamental Properties of the Dielectric Function......Page 39
d) Penetration Depth of Electromagnetic Waves in Metals......Page 41
2.1.2 Quasistatic Response of a Small Metal Sphere to an Electric Field......Page 43
2.1.3 Exact Electrodynamic Calculation of Spherical Metal Clusters (Mie Theory)......Page 46
a) Response of Metal Spheres......Page 48
b) Positions and Shapes of Plasma Resonances......Page 50
c) Resonances of Special Metals......Page 55
d) Extrinsic Cluster Size Effects......Page 61
2.1.4 Extensions of the Mie Theory......Page 73
a) Nonspherical Cluster Shapes......Page 74
b) Core-Shell Particles (Spherical Hetero-Systems)......Page 78
c) Substrate Effects......Page 81
d) Near Fields and Surface Enhanced Raman Scattering......Page 83
e) Nonlinear Optical Effects......Page 89
f) Nonlocal Response and Additional Surface Absorption......Page 92
g) Longitudinal Plasmons......Page 95
2.2 Single Clusters: Intrinsic Size Effects of the Optical Properties......Page 96
a) General Remarks......Page 98
b) Classical Models for $\varepsilon(\omega,R)$......Page 99
c) Quantum-Mechanical Models for $\varepsilon(\omega,R)$......Page 108
2.2.2 Direct Quantum-Mechanical Calculations of the Optical Response......Page 119
a) Jellium Approximation Methods......Page 121
b) Quantum Chemical Methods......Page 128
c) Widths and Shapes of the Resonances......Page 134
2.2.3 Effects of Lower-Lying Electrons......Page 138
2.3 Cluster Matter......Page 143
a) Topological and Optical Characteristics of Cluster Matter......Page 144
b) The Effective Field......Page 153
2.3.2 Statistically Distributed Single Clusters: Effective Medium Theories......Page 155
a) Survey of Effective Medium Concepts......Page 157
b) Derivation of the Genzel $\varepsilon_{\mbox{eff}}$......Page 167
c) Bounds of $\varepsilon_{\mbox{eff}}$......Page 170
e) Effective Media with Optically Nonlinear Clusters or Matrices......Page 172
2.3.3 Separated Cluster Aggregates: Quasi-Static and Electrodynamic Calculations......Page 175
a) Quasi-Static Approximation......Page 177
b) The Cluster Pair......Page 178
c) The Linear Cluster Triplet and Linear Cluster Chains......Page 180
d) Dipole Coupling in Single Extended Cluster Arrays......Page 181
e) The General Case: Generalized Mie Theory (GMT)......Page 184
2.3.4 Densely Packed Mixtures of Clusters and Aggregates......Page 191
a) Combination of Separated Single Clusters and Aggregates......Page 192
b) Other Statistical Concepts......Page 194
c) The Bergman Effective Dielectric Function......Page 197
2.3.5 Nanostructured Matter......Page 204
2.4.1 Large Clusters: Surface Plasmons......Page 207
2.4.2 Small and Very Small Clusters: What is a Plasmon?......Page 213
3.1 General Remarks......Page 223
3.2 Preparation of Metal Clusters......Page 227
3.2.1 General Remarks......Page 228
3.2.2 Free Clusters......Page 232
3.2.3 Clusters on Surfaces......Page 234
a) Matrix Isolation, Color Centers, Photographic Materials......Page 236
b) Glasses and Polymers......Page 238
c) Other Methods......Page 239
3.2.5 Clusters in Liquids......Page 240
3.2.6 Ligand Stabilized Clusters......Page 246
a) Coagulation Aggregates......Page 251
b) Coalescence Aggregates......Page 252
3.2.8 Dense Cluster Matter......Page 253
3.3 Characterization of Metal Clusters......Page 254
3.3.1 General Remarks......Page 255
3.3.2 Clusters in Beams......Page 256
a) Transmission Electron Microscopy......Page 258
b) Electron Diffraction......Page 265
c) Other Methods......Page 266
d) Cluster Matter......Page 270
3.4.1 Common Methods......Page 275
3.4.2 Other Techniques......Page 279
3.4.3 Experimental Measures for Absorption, Scattering, and Extinction......Page 280
3.4.4 Advantages and Drawbacks......Page 285
3.5 Destructive Spectroscopies......Page 286
3.5.1 Two Photon Ionization......Page 287
3.5.2 Beam Depletion Spectroscopy......Page 290
3.5.3 Dissociation Spectroscopy of Supported Clusters......Page 292
3.5.4 Advantages and Drawbacks......Page 293
4. Experimental Results and Discussion......Page 295
a) Smokes......Page 298
b) Beams......Page 301
c) Incandescent Radiation from Clusters......Page 304
a) General Remarks......Page 305
b) Experimental Verification of Mie's Theory......Page 306
c) Mie Dipole Resonance: Position, Width, the $1/R$-effect, and Chemical Interface Damping (CID)......Page 314
d) Spherical Clusters in Various Matrices......Page 322
e) Ellipsoidal Clusters......Page 325
f) The Dielectric Function of Cluster Material and Structural Phase Transitions......Page 327
g) Size Effects in the Temperature Dependence of the Cluster Absorption......Page 337
4.1.3 Large Clusters on Supports......Page 341
a) Thin Films......Page 342
b) Verification of Theoretical Approaches......Page 343
c) Shape and Substrate Effects......Page 344
d) Surface Plasmon Induced Desorption......Page 348
a) Trimers......Page 353
b) Very Small Clusters......Page 354
c) Between Small and Large Clusters......Page 362
d) Pico- and Femtosecond Spectroscopy......Page 369
4.2.2 Small and Very Small Clusters in Matrices......Page 371
a) Experiments Concerning Photography......Page 372
b) Chemically Prepared Ligand Stabilized Clusters......Page 373
c) Physically Prepared Clusters......Page 378
b) From Very Small to Small Spheres and Ellipsoids......Page 384
4.3.1 From Molecular to Metallic Clusters: Covering all Size Ranges......Page 386
4.3.2 Heterogeneous Clusters......Page 391
a) Binary Ag/Au Systems: Nucleus/Shell and Homogeneous Alloy Clusters......Page 392
b) Dielectric Core Clusters......Page 394
c) Other Shell Clusters......Page 395
4.3.3 SERS from Cluster Samples......Page 396
a) General Remarks......Page 400
b) Experiments......Page 402
c) Conclusions......Page 406
a) Second Order Processes......Page 407
b) Third Order Processes......Page 408
4.3.6 Light Emission by Nonoptical Excitation......Page 409
a) Electroluminescence......Page 411
c) Excitation with Tunneling Electrons......Page 413
4.4 Cluster Matter......Page 415
a) Comparison to Effective Medium Theories......Page 417
b) Higher Order Extinction Processes......Page 423
c) Coagulation Effects......Page 427
d) Quantitative Comparison to Direct Electrodynamic Calculations......Page 433
e) Light-Induced Aggregation......Page 438
4.4.2 Coalescence Effects......Page 440
a) The Oseen Transition......Page 445
b) Transition to Compact Thin Films......Page 452
A.1 Tables: Optical Spectroscopy Experiments with Metal Clusters......Page 457
A.2 Survey of Optical Spectra of Elemental Metal Clusters and Chain-Aggregates......Page 471
A.3 Mie Computer Program......Page 493
References......Page 503
Subject Index......Page 547
Springer Series in Materials Science......Page 553