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Condensed-Phase Molecular Spectroscopy and Photophysics

ISBN: 978-0-470-94670-1
344 pages
December 2012
Condensed-Phase Molecular Spectroscopy and Photophysics (0470946709) cover image

An introduction to one of the fundamental tools in chemical research—spectroscopy and photophysics in condensed-phase and extended systems

A great deal of modern research in chemistry and materials science involves the interaction of radiation with condensed-phase systems such as molecules in liquids and solids as well as molecules in more complex media, molecular aggregates, metals, semiconductors, and composites. Condensed-Phase Molecular Spectroscopy and Photophysics was developed to fill the need for a textbook that introduces the basics of traditional molecular spectroscopy with a strong emphasis on condensed-phase systems. It also examines optical processes in extended systems such as metals, semiconductors, and conducting polymers, and addresses the unique optical properties of nanoscale systems.

Condensed-Phase Molecular Spectroscopy and Photophysics begins with an introduction to quantum mechanics that sets a solid foundation for understanding the text's subsequent topics, including:

  • Electromagnetic radiation and radiation-matter interactions
  • Molecular vibrations and infrared spectroscopy
  • Electronic spectroscopy
  • Photophysical processes and light scattering
  • Nonlinear and pump-probe spectroscopies
  • Electron transfer processes

Each chapter contains problems ranging from simple to complex, enabling readers to gradually build their skills and problem-solving abilities. Written for upper-level undergraduate and graduate courses in physical and materials chemistry, this text is uniquely designed to equip readers to solve a broad array of current problems and challenges in chemistry.

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Preface xi

1 Review of Time-Independent Quantum Mechanics 1

1.1 States, Operators, and Representations 1

1.2 Eigenvalue Problems and The Schrödinger Equation 4

1.3 Expectation Values, Uncertainty Relations 6

1.4 The Particle in a Box 7

1.5 Harmonic Oscillator 9

1.6 The Hydrogen Atom and Angular Momentum 12

1.7 Approximation Methods 15

1.8 Electron Spin 18

1.9 The Born-Oppenheimer Approximation 22

1.10 Molecular Orbitals 22

1.11 Energies and Time Scales, Separation of Motions 25

Further Reading 26

Problems 27

2 Electromagnetic Radiation 31

2.1 Classical Description of Light 31

2.2 Quantum Mechanical Description of Light 35

2.3 Fourier Transform Relationships Between Time and Frequency 38

2.4 Blackbody Radiation 40

2.5 Light Sources for Spectroscopy 42

References and Further Reading 44

Problems 44

3 Radiation-Matter Interactions 47

3.1 The Time-Dependent Schrödinger Equation 47

3.2 Time-Dependent Perturbation Theory 50

3.4 Interaction of Matter with the Classical Radiation Field 54

3.5 Interaction of Matter with the Quantized Radiation Field 59

References and Further Reading 63

Problems 64

4 Absorption and Emission of Light 67

4.1 Einstein Coefficients for Absorption and Emission 67

4.2 Other Measures of Absorption Strength 69

4.3 Radiative Lifetimes 72

4.4 Oscillator Strengths 73

4.5 Local Fields 73

Further Reading 74

Problems 75

5 System-Bath Interactions 79

5.1 Phenomenological Treatment of Relaxation and Lineshapes 79

5.2 The Density Matrix 86

5.3 Density Matrix Methods in Spectroscopy 90

5.4 Exact Density Matrix Solution for a Two-Level System 95

References and Further Reading 98

Problems 98

6 Symmetry Considerations 103

6.1 Qualitative Aspects of Molecular Symmetry 103

6.2 Introductory Group Theory 104

6.3 Finding the Symmetries of Vibrational Modes of a Certain Type 109

6.4 Finding the Symmetries of All Vibrational Modes 111

Further Reading 113

Problems 113

7 Molecular Vibrations and Infrared Spectroscopy 115

7.1 Vibrational Transitions 115

7.2 Diatomic Vibrations 117

7.3 Anharmonicity 118

7.4 Polyatomic Molecular Vibrations; Normal Modes 121

7.5 Symmetry Considerations 127

7.6 Isotopic Shifts 130

7.7 Solvent Effects on Vibrational Spectra 130

References and Further Reading 135

Problems 135

8 Electronic Spectroscopy 139

8.1 Electronic Transitions 139

8.2 Spin and Orbital Selection Rules 141

8.3 Spin-Orbit Coupling 143

8.4 Vibronic Structure 143

8.5 Vibronic Coupling 148

8.6 The Jahn-Teller Effect 151

8.7 Considerations in Large Molecules 152

8.8 Solvent Effects on Electronic Spectra 154

Further Reading 159

Problems 160

9 Photophysical Processes 163

9.1 Jablonski Diagrams 163

9.2 Quantum Yields and Lifetimes 166

9.3 Fermi’s Golden Rule for Radiationless Transitions 167

9.4 Internal Conversion and Intersystem Crossing 167

9.5 Intramolecular Vibrational Redistribution 173

9.6 Energy Transfer 179

9.7 Polarization and Molecular Reorientation in Solution 182

References and Further Reading 186

Problems 186

10 Light Scattering 191

10.1 Rayleigh Scattering from Particles 191

10.2 Classical Treatment of Molecular Raman and Rayleigh Scattering 193

10.3 Quantum Mechanical Treatment of Molecular Raman and Rayleigh Scattering 195

10.4 Nonresonant Raman Scattering 204

10.5 Symmetry Considerations and Depolarization Ratios in Raman Scattering 206

10.6 Resonance Raman Spectroscopy 207

References and Further Reading 211

Problems 211

11 Nonlinear and Pump-Probe Spectroscopies 215

11.1 Linear and Nonlinear Susceptibilities 215

11.2 Multiphoton Absorption 216

11.3 Pump-Probe Spectroscopy: Transient Absorption and Stimulated Emission 219

11.4 Vibrational Oscillations and Impulsive Stimulated Scattering 225

11.5 Second Harmonic and Sum Frequency Generation 227

11.6 Four-Wave Mixing 232

11.7 Photon Echoes 232

References and Further Reading 234

Problems 234

12 Electron Transfer Processes 239

12.1 Charge-Transfer Transitions 239

12.2 Marcus Theory 243

12.3 Spectroscopy of Anions and Cations 247

References and Further Reading 248

Problems 248

13 Collections of Molecules 251

13.1 Van Der Waals Molecules 251

13.2 Dimers and Aggregates 252

13.3 Localized and Delocalized Excited States 253

13.4 Conjugated Polymers 256

References 259

Problems 259

14 Metals and Plasmons 263

14.1 Dielectric Function of a Metal 263

14.2 Plasmons 266

14.3 Spectroscopy of Metal Nanoparticles 268

14.4 Surface-Enhanced Raman and Fluorescence 270

References and Further Reading 274

Problems 275

15 Crystals 277

15.1 Crystal Lattices 277

15.2 Phonons in Crystals 281

15.3 Infrared and Raman Spectra 284

15.4 Phonons in Nanocrystals 286

References and Further Reading 287

Problems 287

16 Electronic Spectroscopy of Semiconductors 291

16.1 Band Structure 291

16.2 Direct and Indirect Transitions 296

16.3 Excitons 296

16.4 Defects 298

16.5 Semiconductor Nanocrystals 298

Further Reading 302

Problems 302

Appendices

A Physical Constants, Unit Systems and Conversion Factors 305

B Miscellaneous Mathematics Review 309

C Matrices and Determinants 313

D Character Tables for Some Common Point Groups 317

E Fourier Transforms 321

Index 323

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ANNE MYERS KELLEY earned a BS in chemistry from the University of California, Riverside, in 1980 and a PhD in biophysical chemistry from the University of California, Berkeley, in 1984. Following postdoctoral work at the University of Pennsylvania, she held faculty positions at the University of Rochester (1987–1999) and Kansas State University (1999–2003) before becoming one of the founding faculty at the University of California, Merced, in 2003. Her primary research area has been resonance Raman spectroscopy, linear and nonlinear, but she has also worked in several other areas of spectroscopy including single-molecule and line-narrowed fluorescence, four-wave mixing, and time-resolved methods. She is a Fellow of the American Physical Society and the American Association for the Advancement of Science.

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