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INTRODUCTION TO NONLINEAR OPTICAL EFFECTS IN MOLECULES AND POLYMERS

PARAS N. PRASAD Photonics Research Laboratory Department of Chemistry State University of New York Buffalo, New York and DAVID J. WILLIAMS Corporate Research Laboratories Eastman Kodak Company Rochester, New York

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A Wiley-Interscience Publication JOHN WILEY & SONS, Inc. New York • Chichester • Brisbane • Toronto • Singapore

5 Interaction of Light with a Medium. 5 Scope of This Book.3 1. 2 Basic Research Opportunities. Introduction 1. 15 The Anharmonic Oscillator Model for Nonlinear Optical Effects.3 Equivalent Internal Field Model.5 Nonlinear Optics and Photonics.1 2. Origin of Microscopic Nonlinearity in Organic Systems 3.1 Microscopic Nonlinearity. 24 2.CONTENTS 1.2 2.8 Symmetry. 1 Nonlinear Optical Materials. 21 2. 12 Nonlinear Optical Media. 27 Appendix. 33 8 3. Basis and Formulation of Nonlinear Optics 2.2 1.2 Brief Review of o and n Electrons and Bonding.1 1. 35 3.3 2.6 Anisotropie Media. 5 Multidisciplinary Research. 29 References. 10 The Harmonie Oscillator Model for Linear Optical Processes. 39 35 vii . 6 1 2. 36 3. 19 2.7 Tensors.4 2.4 1. 8 Light Propagation through an Optical Medium.

4 Kurtz Powder Technique.3.. 52 3.4 Parametric Oscillator. 100 5. 96 5.5.3 Sum-over-States Approach. 104 References.2 Second-Harmonic Generation. 121 6.3.6 Relation of xi3) between Film-Based and Laboratory-Based Coordinate Systems.1 Electric Field-Induced Second-Harmonic Generation Method. 53 3. 73 4.1 General Considerations.5. 80 References.4 Additivity Model for Molecular Hyperpolanzabilities.2 Parametric Up-conversion. 102 5. 66 4.1 Derivative versus Sum-over-States Method. 114 6.4.1 Induced Polarization. 60 4. Measurement Techniques for Second-Order Nonlinear Optical Effects 6. 42 3.3 Parametric Processes. 104 6. and Langmuir-Blodgett Films. 99 5.1 Electrooptic Effect. 131 82 59 106 . 85 5.6 Orientational Nonlnearity. Second-Order Nonlinear Optical Processes 5. 59 4.1 Sum-Frequency Generation.3 Methods for Measuring x<2\ 117 6.5 Electrooptic Measurements. 54 3.3.2 Relationship between Microscopic and Macroscopic Nonlinearities in Crystals.4 Low-Frequency Effects. 56 References.viii CONTENTS 3. 122 References.5.5 Quantum-Chemical Approaches. 44 3.5 The Free-Electron Model.5. 98 5.4 Two-Level Model. 42 3. 82 5.4 Langmuir-Blodgett Films. 40 3.3 Difference-Frequency Generation. 57 4. 96 5.5. Polymers. 106 6.3 Poled Polymers.2 Optical Rectification.2 Solvatochromic Measurements. 80 5. 77 4. Bulk Nonlinear Optical Susceptibility 4.2 Derivative Methods.3.4.5 Third-Order Susceptibilities in Crystals. 102 5.

1.4 Degenerate Four-Wave Mixing. 216 9.CONTENTS ix 7. y.3 Two-Photon Absorption.1 Perspective.2. 177 8.2 Selective Measurement Techniques.1 Third-Harmonic Generation. 201 9.5 Langmuir-Blodgett Films. 180 8.2 Third-Harmonic Generation. 176 8. 195 8. Third-Order Nonlinear Optical Processes 8.2.3 Degenerate Four-Wave Mixing.2. 209 9.2 Electric Field-Induced Second-Harmonic Generation.1 Third-Harmonic Generation.1 Perspective. 178 8.8 Cascading Effect. 211 9. 214 9. 218 References.5 Coherent Raman Effects.1 A General Discussion of the Measurement of xi3\ 199 9.1 The Various Third-Order Processes and Resulting Polarizations.7 Intensity-Dependent Phase Shift. 205 9.2 Structural Requirements for Third-Order Optical Nonlinearity. Measurement Techniques for Third-Order Nonlinear Optical Effects 9. 224 132 175 199 222 .3 Measurement of Microscopic Nonlinearities.1. 184 8.2 Structural Requirements for Second-Order Optical Nonlinearity. 184 8. 220 10. 222 10.1. A Survey of Third-Order Nonlinear Optical Materials 10.3 Crystals and Inclusion Complexes.2. 196 References. 160 References. 152 7. 134 7.4 Poled Polymers.3 Electric Field-Induced Second-Harmonic Generation.5 Resonant Nonlinearity.2.6 Other Mechanisms Contributing to the Intensity Dependence of the Refractive Index. 132 7. 178 8.2.5 Self-Focusing Methods. 178 8.2. 188 8. 201 9.7 Nonlinear Fabry-Perot Method. 170 8.6 Surface Plasmon Nonlinear Optics. 197 9.1. 205 9. 175 8. 194 8.4 Optical Kerr Gate.1. A Survey of Second-Order Nonlinear Optical Materials 7.2 Self-Action. 143 7.4 Degenerate Four-Wave Mixing.

279 12. 282 12.1 13.3.3 Second-Order Nonlinear Optical Processes.4.4. 261 11.6 Polysilanes. 241 10.5 Optical Bistability. 293 13.5 Other Conjugated Polymers. 239 10. 245 10. Issues and Future Directions 13. 297 Materials for Second-Order Nonlinear Optics. Device Concepts 12. 225 10.1 Second-Harmonic Generation in a Planar Waveguide. 281 12.1 Polydiacetylenes. 302 303 305 252 272 295 Appendix: Units Index .4 Polythiophene.4 Microscopic Processes. 277 12. 231 10.3 Light Modulation.4.4 Conjugated Polymers. 258 11. Nonlinear Optics in Optical Waveguides and Fibers 11.2 Phase Matching in a Periodically Poled Waveguide.2 Nonlinear Optics with Guided Waves. 231 10.3 13.1 Spatial Light Modulators.3 Second-Harmonic Generation in Organic Crystal Cored Fibers.4 Optical Switching.3. 252 11.6 Sensor Protection.2 Poly-p-phenylene Vinylenes and Analogues.4.7 Organometallic Structures.4. 263 11.2 Mach-Zehnder Interferometer. 292 References. 268 References. 243 10.3.5 Macrocycles. 256 11.2 13.x CONTENTS 10. 272 12. 264 11. 297 Materials for Third-Order Nonlinear Optics. 274 12.1 Basic Concepts of Guided Waves.3 Liquid Materials and Solutions. 285 12.7 Optical Phase Conjugation. 235 10.2 Frequency Conversion.5 Material Requirements for Waveguides. 248 11. 290 12.3. 258 11.1 Introduction. 270 12. 296 Local Fields. 246 References.3. 300 References. 238 10.3 Polyacetylene.4 Third-Order Nonlinear Optical Processes.