Spectroscopy of Condensed Media: Dynamics of Molecular Interactions

Spectroscopy of Condensed Media: Dynamics of Molecular Interactions discusses the use of molecular spectroscopy (including nuclear magnetic resonance [NMR] and nonlinear optical spectroscopy) in dynamic processes in condensed molecular systems. The book reviews relationship between transition probability and the time-correlation function of an isotropic electric dipole system, linear-response theory, and light scattering resulting from the translational motion of molecules in fluids. The text describes molecular rotation, theories of angular momentum, nuclear magnetic resonance, and spontaneous and coherent Raman effects. Closely related with the Raman and Brillouin scattering are vibrational dephasing, relaxation processes, and dynamics of phase transition solids. The book highlights the advantages of using NMR and also explains the basic concepts, such as local field, spin temperature, and effective Hamiltonians, that are employed in interpreting NMR experiments. The investigator can use nonlinear optical spectroscopy to study condensed matter. The text also cites two methods in which the investigator can control the time-dependent average Hamiltonian by (1) manipulating the intensity, timing, phase of the pulses, or (2) by sample spinning. The book is intended for advanced graduate students in physical chemistry that will equally benefit both investigators and scientists involved in physics research.

Table of Contents:
Preface1 Time-Correlation Functions and Spectroscopy 1.1 Introduction 1.2 Stationary Random Process and Time-Correlation Functions 1.3 Spectral Power Density and the Wiener-Khintchine Theorem 1.4 Absorption Line Shape and the Dipole-Dipole Time-Correlation Function 1.5 The Liouville Equation of Motion 1.6 Linear-Response Theory 1.7 Fluctuation-Dissipation Theorem 1.8 Absorption of Radiation by a System of Electric Dipoles 1.9 Spectral Moments and Cumulants 1.10 Stochastic Theory of Line Shape 1.11 The Distribution-Function Method for the Random Process2 Spontaneous Scattering of Light in Condensed Media 2.1 Introduction 2.2 Inhomogeneous Wave Equation for the Scattered Field 2.3 Spectral Power Density and the Polarizability Density Time-Correlation Function 2.4 Light Scattering from Translational Motion 2.5 Translational Diffusion of Macromolecules in Dilute Solution 2.6 Light Scattering from Translational Motion of a Pure Dense Fluid 2.7 Hydrodynamic Equation 2.8 Solution of Hydrodynamic Equations and Interpretation of the Rayleigh-Brillouin Spectrum of a Viscous Fluid 2.9 Viscoelastic Liquids 2.10 Static-Structure Factor and Longitudinal Compliance 2.11 Critical Opalescence 2.12 Scattering of Light from Fluids of Optically Anisotropic Molecules 2.13 Coupling of Polarizability Anisotropy to Transverse Waves 2.14 Photoelastic Effects 2.15 Raman Scattering3 Angular Momentum and Molecular Rotation 3.1 Introduction 3.2 Rotation Matrix 3.3 Spherical-Harmonics Addition Theorem 3.4 Irreducible Spherical Tensors 3.5 Raman-Scattering Intensity and the Orientation Parameters 3.6 Studies of Reorientational Motion by Depolarized Rayleigh and Raman Scattering 3.7 Models for Calculating the Reorientational Time-Correlation Function 3.8 Stochastic Theory of Molecular Reorientation 3.9 Rotational-Diffusion Model 3.10 Orientational Time-Correlation Functions of the Rotational-Diffusion Model 3.11 Other Molecular-Reorientation Models 3.12 Wigner-Eckart Theorem 3.13 Electronic Quadrupole Effect4 The Time-Correlation Function and the Memory-Function Formalism 4.1 Introduction 4.2 The Memory Function 4.3 The Generalized Langevin Equation 4.4 Time-Correlation Function Matrices 4.5 Microscopic Theory for Brownian Motion 4.6 Spatial Dependence of the Time-Correlation Function 4.7 Hydrodynamic Approximation and Relaxation Times 4.8 Generalized Hydrodynamics of the Momentum Density 4.9 Symmetry Consideration 4.10 Generalized Hydrodynamics Theory of the Isotropic Light-Scattering Spectrum 4.11 Generalized Hydrodynamics Theory of the Depolarized Light-Scattering Spectrum 4.12 Light Scattering from Viscoelastic Liquids 4.13 Single-Particle and Collective Orientational-Relaxation Times5 Nuclear Magnetic Resonance Spectroscopy 5.1 Introduction 5.2 Motion of Free Spins 5.3 The Bloch Equations 5.4 Steady-State Solution of the Bloch Equations and Saturation 5.5 Dipolar Interaction in a Rigid Lattice 5.6 Free-Induction Decay and Absorption Line Shape 5.7 Spin Echoes in Dipolar Solids 5.8 High-Resolution NMR of Solids 5.9 Spin Temperature and Double Resonance in the Rotating Frame 5.10 Spin-Lattice Relaxation in Solids and its Effect on Spin Temperature 5.11 Spin-Lattice Relaxation in the Rotating Frame 5.12 A General Relaxation Theory for Random Perturbations6 Linear and Nonlinear Raman Spectroscopy of the Condensed Phase 6.1 Introduction 6.2 Raman Polarizability Tensor 6.3 Harmonic Approximation 6.4 Correlation Functions of Isotropic Raman Polarizability in Dense Molecular Fluids 6.5 Dephasing and Population Relaxation 6.6 Raman and Brillouin Scattering from Soft Modes Associated with Phase Transitions in Solids 6.7 Nonlinear Optics and Coherent Raman Spectroscopy 6.8 Stimulated Raman Scattering 6.9 Coherent Anti-Stokes-Raman Spectroscopy 6.10 Raman-Induced Kerr-Effect Spectroscopy 6.11 Optical Heterodyned Raman-Induced Kerr Effect 6.12 Quantum Theory of Nonlinear Susceptibility 6.13 Relation of CARS to Spontaneous Ranian ScatteringAppendix: Linear-Response Theory and Fluctuation-Dissipation Theorem Including the Spatial Dependence A.1 Derivation of a Generalized Linear-Response Function A.2 Generalized Susceptibility Tensor ? ij(q, ?) A.3 Linear-Response Theory in Terms of an Initial Value Problem A.4 Fluctuation-Dissipation Theorem A.5 Application to Linear Viscoelastic SystemsReferencesIndex