现代光谱学PDF电子书下载

1 Introduction 1

1.1 Overview 1

1.2 The Beer-Lambert Law 3

1.3 Regions of the Electromagnetic Spectrum 4

1.4 Absorption Spectra of Proteins and Nucleic Acids 6

1.5 Absorption Spectra of Mixtures 8

1.6 The Photoelectric Effect 9

1.7 Techniques for Measuring Absorbance 10

1.8 Pump-Probe and Photon-Echo Experiments 13

1.9 Linear and Circular Dichroism 15

1.10 Distortions of Absorption Spectra by Light Scattering or Nonuniform Distributions of the Absorbing Molecules 17

1.11 Fluorescence 19

1.12 IR and Raman Spectroscopy 24

1.13 Lasers 25

1.14 Nomenclature 26

2 Basic Concepts of Quantum Mechanics 29

2.1 Wavefunctions,Operators,and Expectation Values 29

2.1.1 Wavefunctions 29

2.1.2 Operators and Expectation Values 30

2.2 The Time-Dependent and Time-Independent Schr？dinger Equations 36

2.2.1 Superposition States 41

2.3 Spatial Wavefunctions 42

2.3.1 A Free Particle 42

2.3.2 A Particle in a Box 43

2.3.3 The Harmonic Oscillator 46

2.3.4 Atomic Orbitals 48

2.3.5 Molecular Orbitals 51

2.3.6 Approximate Wavefunctions for Large Systems 57

2.4 Spin Wavefunctions and Singlet and Triplet States 57

2.5 Transitions Between States：Time-Dependent Perturbation Theory 65

2.6 Lifetimes of States and the Uncertainty Principle 68

3 Light 73

3.1 Electromagnetic Fields 73

3.1.1 Electrostatic Forces and Fields 73

3.1.2 Electrostatic Potentials 74

3.1.3 Electromagnetic Radiation 76

3.1.4 Energy Density and Irradiance 83

3.1.5 The Complex Electric Susceptibility and Refractive Index 90

3.1.6 Local-Field Correction Factors 94

3.2 The Black-Body Radiation Law 96

3.3 Linear and Circular Polarization 98

3.4 Quantum Theory of Electromagnetic Radiation 100

3.5 Superposition States and Interference Effects in Quantum Optics 104

3.6 Distribution of Frequencies in Short Pulses of Light 106

4 Electronic Absorption 109

4.1 Interactions of Electrons with Oscillating Electric Fields 109

4.2 The Rates of Absorption and Stimulated Emission 113

4.3 Transition Dipoles and Dipole Strengths 118

4.4 Calculating Transition Dipoles forπMolecular Orbitals 126

4.5 Molecular Symmetry and Forbidden and Allowed Transitions 128

4.6 Linear Dichroism 142

4.7 Configuration Interactions 148

4.8 Calculating Electric Transition Dipoles with the Gradient Operator 152

4.9 Transition Dipoles for Excitations to Singlet and Triplet States 161

4.10 The Born-Oppenheimer Approximation,Franck-Condon Factors,and the Shapes of Electronic Absorption Bands 163

4.11 Spectroscopic Hole-Burning 171

4.12 Effects of the Surroundings on Molecular Transition Energies 174

4.13 The Electronic Stark Effect 182

5 Fluorescence 189

5.1 The Einstein Coefficients 189

5.2 The Stokes Shift 192

5.3 The Mirror-Image Law 195

5.4 The Strickler-Berg Equation and Other Relationships Between Absorption and Fluorescence 197

5.5 Quantum Theory of Absorption and Emission 203

5.6 Fluorescence Yields and Lifetimes 208

5.7 Fluorescent Probes and Tags 214

5.8 Photobleaching 218

5.9 Fluorescence Anisotropy 219

5.10 Single-Molecule Fluorescence and High-Resolution Fluorescence Microscopy 225

5.11 Fluorescence Correlation Spectroscopy 231

5.12 Intersystem Crossing,Phosphorescence,and Delayed Fluorescence 238

6 Vibrational Absorption 241

6.1 Vibrational Normal Modes and Wavefunctions 241

6.2 Vibrational Excitation 247

6.3 IR Spectroscopy of Proteins 253

6.4 Vibrational Stark Effects 256

7 Resonance Energy Transfer 259

7.1 Introduction 259

7.2 The F？rster Theory 261

7.3 Exchange Coupling 275

7.4 Energy Transfer to and from Carotenoids in Photosynthesis 277

8 Exciton Interactions 281

8.1 Stationary States of Systems with Interacting Molecules 281

8.2 Effects of Exciton Interactions on the Absorption Spectra of Oligomers 290

8.3 Transition-Monopole Treatments of Interaction Matrix Elements and Mixing with Charge-Transfer Transitions 295

8.4 Exciton Absorption Band Shapes and Dynamic Localization of Excitations 298

8.5 Exciton States in Photosynthetic Antenna Complexes 301

8.6 Excimers and Exciplexes 304

9 Circular Dichroism 307

9.1 Magnetic Transition Dipoles and n-π Transitions 307

9.2 The Origin of Circular Dichroism 317

9.3 Circular Dichroism of Dimers and Higher Oligomers 322

9.4 Circular Dichroism of Proteins and Nucleic Acids 328

9.5 Magnetic Circular Dichroism 332

10 Coherence and Dephasing 335

10.1 Oscillations Between Quantum States of an Isolated System 335

10.2 The Density Matrix 339

10.3 The Stochastic Liouville Equation 344

10.4 Effects of Stochastic Relaxations on the Dynamics of Quantum Transitions 346

10.5 A Density-Matrix Treatment of Steady-State Absorption 352

10.6 The Relaxation Matrix 355

10.7 More General Relaxation Functions and Spectral Lineshapes 364

10.8 Anomalous Fluorescence Anisotropy 370

11 Pump-Probe Spectroscopy,Photon Echoes,and Vibrational Wavepackets 377

11.1 First-Order Optical Polarization 377

11.2 Third-Order Optical Polarization and Nonlinear Response Functions 386

11.3 Pump-Probe Spectroscopy 391

11.4 Photon Echoes 395

11.5 Transient Gratings 401

11.6 Vibrational Wavepackets 404

11.7 Wavepacket Pictures of Spectroscopic Transitions 413

12 Raman Scattering and Other Multiphoton Processes 417

12.1 Types of Light Scattering 417

12.2 The Kramers-Heisenberg-Dirac Theory 422

12.3 The Wavepacket Picture of Resonance Raman Scattering 430

12.4 Selection Rules for Raman Scattering 432

12.5 Surface-Enhanced Raman Scattering 435

12.6 Biophysical Applications of Raman Spectroscopy 436

12.7 Coherent Raman Scattering 437

12.8 Multiphoton Absorption 439

12.9 Quasielastic(Dynamic)Light Scattering(Photon Correlation Spectroscopy) 442

Appendix 1-Vectors 447

Appendix 2-Matrices 451

Appendix 3-Fourier Transforms 455

Appendix 4-Fluorescence Phase Shift and Modulation 459

Appendix 5-CGS and SI Units and Abbreviations 463

References 465

Subject Index 505