Preface |
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xiii | |
Acknowledgments |
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xv | |
Foreword |
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xvii | |
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3 | (9) |
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3 | (1) |
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1.2 Response Functions and Fluctuations |
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4 | (2) |
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1.3 Time-Correlation Functions |
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6 | (1) |
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1.4 Linear Response Theory |
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6 | (2) |
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1.5 Fluctuation-Dissipation Theorem |
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8 | (1) |
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1.6 Diffusion, Friction, and Viscosity |
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8 | (2) |
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10 | (2) |
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2 Phenomenological Description of Relaxation in Liquids |
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12 | (7) |
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12 | (1) |
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13 | (1) |
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2.3 Fokker-Planck Equation |
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14 | (1) |
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2.4 Smoluchowski Equation |
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15 | (1) |
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16 | (1) |
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2.6 The Special Case of Harmonic Potential |
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16 | (1) |
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17 | (2) |
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3 Density and Momentum Relaxation in Liquids |
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19 | (13) |
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19 | (1) |
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3.2 Hydrodynamics at Large Length Scales |
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20 | (4) |
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3.2.1 Rayleigh-Brillouin Spectrum |
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22 | (2) |
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3.3 Hydrodynamic Relations between Self-Diffusion Coefficient and Viscosity |
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24 | (1) |
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3.4 Slow Dynamics at Large Wave Numbers: de Gennes Narrowing |
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25 | (2) |
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3.5 Extended Hydrodynamics: Dynamics at Intermediate Length Scales |
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27 | (2) |
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29 | (1) |
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30 | (2) |
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4 Relationship between Theory and Experiment |
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32 | (19) |
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32 | (2) |
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4.2 Dynamic Light Scattering: Probe of Density Fluctuation at Long Length Scales |
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34 | (2) |
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4.3 Magnetic Resonance Experiments: Probe of Single-Particle Dynamics |
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36 | (2) |
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38 | (1) |
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4.5 Dielectric Relaxation |
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38 | (1) |
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4.6 Fluorescence Depolarization |
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39 | (1) |
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4.7 Solvation Dynamics (Time-Dependent Fluorescence Stokes Shift) |
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40 | (1) |
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4.8 Neutron Scattering: Coherent and Incoherent |
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41 | (2) |
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4.9 Raman Line-Shape Measurements |
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43 | (2) |
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4.10 Coherent Anti-Stokes Raman Scattering (CARS) |
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45 | (1) |
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45 | (2) |
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4.12 Ultrafast Chemical Reactions |
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47 | (1) |
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4.13 Fluorescence Quenching |
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47 | (1) |
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4.14 Two-Dimensional Infrared (2D-IR) Spectroscopy |
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48 | (1) |
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4.15 Single-Molecule Spectroscopy |
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49 | (1) |
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49 | (2) |
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5 Orientational and Dielectric Relaxation |
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51 | (27) |
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51 | (4) |
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5.2 Equilibrium and Time-Dependent Orientational Correlation Functions |
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55 | (2) |
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5.3 Relationship with Experimental Observables |
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57 | (1) |
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5.4 Molecular Hydrodynamic Description of Orientational Motion |
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57 | (2) |
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5.4.1 The Equations of Motion |
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58 | (1) |
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5.4.2 Limiting Situations |
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59 | (1) |
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5.5 Markovian Theory of Collective Orientational Relaxation: Berne Treatment |
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59 | (9) |
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5.5.1 Generalized Smoluchowski Equation Description |
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60 | (2) |
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5.5.2 Solution by Spherical Harmonic Expansion |
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62 | (2) |
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5.5.3 Relaxation of Longitudinal and Transverse Components |
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64 | (1) |
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5.5.4 Molecular Theory of Dielectric Relaxation |
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64 | (1) |
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5.5.5 Hidden Role of Translational Motion in Orientational Relaxation |
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65 | (1) |
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5.5.6 Orientational de Gennes Narrowing at Intermediate Wave Numbers |
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66 | (1) |
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5.5.7 Reduction to the Continuum Limit |
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67 | (1) |
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5.6 Memory Effects in Orientational Relaxation |
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68 | (2) |
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5.7 Relationship between Macroscopic and Microscopic Orientational Relaxations |
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70 | (2) |
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5.8 The Special Case of Orientational Relaxation of Water |
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72 | (2) |
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5.9 Lattice Models of Orientational Relaxation |
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74 | (1) |
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5.10 Nonassociated Liquids |
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75 | (1) |
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76 | (2) |
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6 Solvation Dynamics in Dipolar Liquid |
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78 | (39) |
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78 | (1) |
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6.2 Physical Concepts and Measurement |
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79 | (7) |
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6.2.1 Measuring Ultrafast, Sub-100 fs Decay |
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83 | (3) |
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6.3 Phenomenological Theories: Continuum-Model Descriptions |
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86 | (7) |
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6.3.1 Homogeneous Dielectric Models |
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86 | (3) |
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6.3.2 Inhomogeneous Dielectric Models |
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89 | (2) |
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6.3.3 Dynamic Exchange Model |
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91 | (2) |
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6.4 Experimental Results: A Chronological Overview |
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93 | (4) |
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6.4.1 Discovery of Multiexponential Solvation Dynamics: Phase-I (1980-1990) |
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93 | (1) |
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6.4.2 Discovery of Subpicosecond Ultrafast Solvation Dynamics: Phase-II (1990-2000) |
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94 | (1) |
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6.4.3 Solvation Dynamics in Complex Systems: Phase-III (2000-) |
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95 | (2) |
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97 | (3) |
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6.5.1 Molecular Hydrodynamics Description |
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97 | (1) |
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6.5.2 Polarization and Dielectric Relaxation of Pure Liquid |
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98 | (1) |
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6.5.2.1 Effects of Translational Diffusion in Solvation Dynamics |
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98 | (2) |
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6.6 Simple Idealized Models |
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100 | (2) |
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6.6.1 Overdamped Solvation: Brownian Dipolar Lattice |
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101 | (1) |
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6.6.2 Underdamped Solvation: Stockmayer Liquid |
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102 | (1) |
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6.7 Solvation Dynamics in Water, Acetonitrile, and Methanol Revisited |
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102 | (4) |
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6.7.1 The Sub-100 fs Ultrafast Component: Microscopic Origin |
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104 | (2) |
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6.8 Effects of Solvation on Chemical Processes in the Solution Phase |
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106 | (5) |
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6.8.1 Limiting Ionic Conductivity of Electrolyte Solutions: Control of a Slow Phenomenon by Ultrafast Dynamics |
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107 | (1) |
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6.8.2 Effects of Ultrafast Solvation in Electron-Transfer Reactions |
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107 | (1) |
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6.8.3 Nonequilibrium Solvation Effects in Chemical Reactions |
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107 | (2) |
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6.8.3.1 Strong Solvent Forces |
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109 | (1) |
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6.8.3.2 Weak Solvent Forces |
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110 | (1) |
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6.9 Solvation Dynamics in Several Related Systems |
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111 | (2) |
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6.9.1 Solvation in Aqueous Electrolyte Solutions |
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111 | (1) |
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6.9.2 Dynamics of Electron Solvation |
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111 | (1) |
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6.9.3 Solvation Dynamics in Supercritical Fluids |
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112 | (1) |
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6.9.4 Nonpolar Solvation Dynamics |
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112 | (1) |
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6.10 Computer Simulation Studies: Simple and Complex Systems |
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113 | (2) |
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114 | (1) |
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6.10.2 Water Pool in Reverse Micelles |
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114 | (1) |
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6.10.3 Protein Hydration Layer |
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114 | (1) |
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6.10.4 DNA Groove Hydration Layer |
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115 | (1) |
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115 | (2) |
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7 Activated Barrier-Crossing Dynamics in Liquids |
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117 | (38) |
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117 | (2) |
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119 | (7) |
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7.2.1 Stochastic Models: Understanding from Eigenvalue Analysis |
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119 | (3) |
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7.2.2 Validity of a Rate-Law Description: Role of Macroscopic Fluctuations |
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122 | (2) |
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7.2.3 Time-Correlation-Function Approach: Separation of Transient Behavior from Rate Law |
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124 | (2) |
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7.3 Transition-State Theory |
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126 | (1) |
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7.4 Frictional Effects on Barrier-Crossing Rate in Solution: Kramers' Theory |
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127 | (5) |
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129 | (1) |
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7.4.2 Limitations of Kramers' Theory |
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130 | (1) |
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7.4.3 Comparison of Kramers' Theory with Experiments |
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131 | (1) |
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7.4.4 Comparison of Kramers' Theory with Computer Simulations |
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132 | (1) |
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7.5 Memory Effects in Chemical Reactions: Grote-Hynes Generalization of Kramers' Theory |
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132 | (11) |
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7.5.1 Frequency Dependence of Friction: General Aspects |
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138 | (1) |
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7.5.1.1 Frequency-Dependent Friction from Hydrodynamics |
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138 | (2) |
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7.5.1.2 Frequency-Dependent Friction from Mode-Coupling Theory |
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140 | (2) |
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7.5.2 Comparison of Grote-Hynes Theory with Experiments and Computer Simulations |
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142 | (1) |
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7.6 Variational Transition-State Theory |
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143 | (1) |
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7.7 Multidimensional Reaction Surface |
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144 | (2) |
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7.7.1 Multidimensional Kramers' Theory |
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145 | (1) |
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7.8 Transition Path Sampling |
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146 | (2) |
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7.9 Quantum Transition-State Theory |
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148 | (1) |
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149 | (6) |
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150 | (5) |
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8 Barrierless Reactions in Solution |
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155 | (25) |
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155 | (3) |
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8.2 Standard Model of Barrierless Reactions |
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158 | (8) |
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8.2.1 Exactly Solvable Models for Photochemical Reactions |
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159 | (1) |
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8.2.1.1 Oster-Nishijima Model |
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160 | (1) |
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161 | (1) |
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8.2.1.3 Pinhole Sink Model |
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162 | (2) |
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8.2.2 Approximate Solutions of Realistic Models |
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164 | (1) |
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8.2.2.1 Delta Function Sink |
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164 | (1) |
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165 | (1) |
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8.3 Inertial Effects in Barrierless Reactions: Viscosity Turnover of Rate |
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166 | (4) |
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8.4 Memory Effects in Barrierless Reactions |
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170 | (2) |
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8.5 Unusual Features of Barrierless Chemical Reactions |
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172 | (2) |
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8.5.1 Excitation Wavelength Dependence |
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172 | (1) |
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8.5.2 Negative Activation Energy |
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172 | (2) |
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8.6 Multidimensional Reaction Potential Energy Surface |
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174 | (1) |
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8.7 Analysis of Experimental Results |
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174 | (3) |
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8.7.1 Photoisomerization and Ground-State Potential Energy Surface |
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174 | (1) |
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8.7.2 Decay Dynamics of Rhodopsin and Isorhodopsin |
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175 | (2) |
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8.7.3 Conflicting Crystal Violet Isomerization Mechanism |
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177 | (1) |
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177 | (3) |
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9 Dynamical Disorder, Geometric Bottlenecks, and Diffusion-Controlled Bimolecular Reactions |
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180 | (15) |
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180 | (1) |
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9.2 Passage through Geometric Bottlenecks |
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181 | (3) |
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9.2.1 Diffusion in a Two-Dimensional Periodic Channel |
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181 | (2) |
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9.2.2 Diffusion in a Random Lorentz Gas |
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183 | (1) |
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184 | (2) |
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9.4 Diffusion over a Rugged Energy Landscape |
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186 | (4) |
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9.5 Diffusion-Controlled Bimolecular Reactions |
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190 | (3) |
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193 | (2) |
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10 Electron-Transfer Reactions |
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195 | (31) |
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195 | (1) |
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10.2 Classification of Electron-Transfer Reactions |
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196 | (1) |
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10.2.1 Classification Based on Ligand Participation |
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196 | (1) |
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10.2.2 Classification Based on Interactions between Reactant and Product Potential Energy Surfaces |
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196 | (1) |
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197 | (11) |
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10.3.1 Reaction Coordinate (RC) |
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198 | (2) |
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10.3.2 Free-Energy Surfaces: Force Constant of Polarization Fluctuation |
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200 | (3) |
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10.3.3 Derivation of ETR Rate |
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203 | (3) |
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10.3.4 Experimental Verification of the Marcus Theory |
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206 | (2) |
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10.4 Dynamical Solvent Effects on ETRs (One-Dimensional Descriptions) |
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208 | (2) |
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10.5 Role of Vibrational Modes in Weakening Solvent Dependence |
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210 | (6) |
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10.5.1 Role of Classical Intramolecular Vibrational Modes: Sumi-Marcus Theory |
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210 | (3) |
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10.5.2 Role of High-Frequency Vibration Modes |
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213 | (2) |
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10.5.3 Hybrid Model of ETR: Crossover from Solvent to Vibrational Control |
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215 | (1) |
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10.6 Theoretical Formulation of Multidimensional Electron Transfer |
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216 | (4) |
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10.7 Effects of Ultrafast Solvation on Electron-Transfer Reactions |
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220 | (1) |
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10.7.1 Absence of Significant Dynamic Solvent Effects on ETR in Water, Acetonitrile, and Methanol |
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220 | (1) |
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221 | (5) |
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222 | (4) |
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11 Forster (or, Fluorescence) Resonance Energy Transfer (FRET) |
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226 | (33) |
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226 | (3) |
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11.2 A Brief Historical Perspective |
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229 | (1) |
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11.3 Derivation of Forster Expression |
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230 | (9) |
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11.3.1 Expressions for Emission (or Fluorescence) Spectrum |
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234 | (3) |
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11.3.2 Absorption Spectrum |
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237 | (1) |
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11.3.3 The Final Forster Expression |
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238 | (1) |
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11.4 Applications of Forster Theory to Chemistry, Biology, and Materials Science |
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239 | (13) |
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11.4.1 FRET-Based Glucose Sensor |
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239 | (1) |
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11.4.2 FRET and Macromolecular Dynamics |
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239 | (4) |
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11.4.3 FRET and Single-Molecule Spectroscopy |
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243 | (4) |
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11.4.4 Beyond Organic Dyes as Donor-Acceptor Pairs |
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247 | (2) |
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11.4.5 FRET and Conjugated Polymers |
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249 | (3) |
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11.5 Beyond Forster Formalism |
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252 | (5) |
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11.5.1 Orientation Factor |
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252 | (1) |
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11.5.2 Point-Dipole Approximation |
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253 | (1) |
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11.5.3 Contribution of Optically Dark States |
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254 | (3) |
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257 | (2) |
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12 Vibrational-Energy Relaxation |
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259 | (21) |
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259 | (2) |
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12.2 Isolated Binary Collision (IBC) Model |
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261 | (2) |
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12.3 Landau-Teller Expression: The Classical Limit |
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263 | (2) |
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12.4 Weak-Coupling Model: Time-Correlation-Function Representation of Transition Probability |
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265 | (3) |
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12.5 Vibrational Relaxation at High Frequency: Quantum Effects |
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268 | (3) |
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12.6 Experimental Studies of Vibrational-Energy Relaxation |
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271 | (1) |
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12.7 Computer-Simulation Studies of Vibrational-Energy Relaxation |
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272 | (3) |
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12.7.1 Vibrational-Energy Relaxation of Water |
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272 | (2) |
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12.7.2 Vibrational-Energy Relaxation in Liquid Oxygen and Nitrogen |
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274 | (1) |
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12.8 Quantum Interference Effects on Vibrational-Energy Relaxation in a Three-Level System: Breakdown of the Rate Equation Description |
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275 | (2) |
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12.9 Vibrational Life Time Dynamics in Supercritical Fluids |
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277 | (2) |
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279 | (1) |
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13 Vibrational-Phase Relaxation |
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280 | (16) |
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280 | (2) |
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13.2 Kubo-Oxtoby Theory of Vibrational Line Shapes |
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282 | (5) |
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13.3 Homogeneous vs. Inhomogeneous Linewidths |
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287 | (2) |
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13.4 Relative Role of the Attractive and Repulsive Forces |
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289 | (1) |
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13.5 Vibration-Rotation Coupling |
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289 | (1) |
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13.6 Experimental Results of Vibrational-Phase Relaxation |
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290 | (2) |
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13.6.1 Semiquantitative Aspects of Dephasing Rates in Solution |
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291 | (1) |
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13.6.2 Subquadratic Quantum Number Dependence |
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291 | (1) |
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13.7 Vibrational Dephasing Near the Gas-Liquid Critical Point |
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292 | (1) |
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13.8 Multidimensional IR Spectroscopy |
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292 | (2) |
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294 | (2) |
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296 | (2) |
Index |
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298 | |