Biman Bagchi

Molecular Relaxation in Liquids

• Gebundenes Buch

Produktbeschreibung

The book captures recent and exciting developments in molecular relaxation in liquids.

Produktdetails

• Verlag: Oxford University Press, USA
• Seitenzahl: 336
• Erscheinungstermin: 17. April 2012
• Englisch
• Abmessung: 241mm x 159mm x 25mm
• Gewicht: 594g
• ISBN-13: 9780199863327
• ISBN-10: 0199863326
• Artikelnr.: 34552306

Autorenporträt

Biman Bagchi is Professor at the Indian Institute of Science in Bangalore, India.

Inhaltsangabe

* Chapter 1. Basic Concepts
* 1.1 Introduction
* 1.2 Response Functions and Fluctuations
* 1.3 Time Correlation Functions
* 1.4 Linear Response Theory
* 1.5 Fluctuation-Dissipation Theorem
* 1.6 Diffusion, Friction and Viscosity
* Chapter 2. Phenomenological Description of Relaxation in Liquids
* 2.1 Introduction
* 2.2 Langevin Equation
* 2.3 Fokker-Planck Equation
* 2.4 Smoluchowski Equation
* 2.5 Master Equations
* 2.6 The Special Case of Harmonic Potential
* Chapter 3. Density and Momentum Relaxation in Liquids
* 3.1 Introduction
* 3.2 Hydrodynamics at Large Length Scales
* 3.2.1 Rayleigh-Brillouin Spectrum
* 3.3 Hydrodynamic Relation Self-diffusion Coefficient and Viscosity
* 3.4 Slow Dynamics at Large Wavenumbers: de Gennes Narrowing
* 3.5 Extended Hydrodynamics: Dynamics at Intermediate Length Scale
* 3.6 Mode Coupling Theory
* Chapter 4. Relationship between Theory and Experiment
* 4.1 Introduction
* 4.2 Dynamic Light Scattering: Probe of Density Fluctuation at Long
Length Scales
* 4.3 Magnetic Resonance Experiments: Probe of Single Particle Dynamics
* 4.4 Kerr Relaxation
* 4.5 Dielectric Relaxation
* 4.6 Fluorescence Depolarization
* 4.7 Solvation Dynamics (Time Dependent Fluorescence Stokes Shift)
* 4.8 Neutron Scattering: Coherent and Incoherent
* 4.9 Raman Lineshape Measurements
* 4.10 Coherent Anti-Stokes Raman Scattering (CARS)
* 4.11 Echo Techniques
* 4.12 Ultrafast Chemical Reactions
* 4.13 Fluorescence Quenching
* 4.14 Two-dimensional Infrared (2D IR) Spectroscopy
* 4.15 Single Molecule Spectroscopy
* Chapter 5. Orientational and Dielectric Relaxation
* 5.1 Introduction
* 5.2 Equilibrium and Time-Dependent Orientational Correlation
Functions
* 5.3 Relationship with Experimental Observables
* 5.4 Molecular Hydrodynamic Description of Orientational Motion
* 5.4.1 The Equations of Motion
* 5.4.2 Limiting Situations
* 5.5 Markovian Theory of Collective Orientational Relaxation: Berne
Treatment
* 5.5.1 Generalized Smoluchowski Equation Description
* 5.5.2 Solution by Spherical Harmonic Expansion
* 5.5.3 Relaxation of Longitudinal and Transverse Components
* 5.5.4 Molecular Theory of Dielectric Relaxation
* 5.5.5 Hidden Role of Translational Motion in Orientational Relaxation
* 5.5.6 Orientational de Gennes Narrowing at Intermediate Wave Numbers
* 5.5.7 Reduction to the Continuum Limit
* 5.6 Memory Effects in Orientational Relaxation
* 5.7 Relationship between Macroscopic and Microscopic Orientational
Relaxations
* 5.8 The Special Case of Orientational Relaxation of Water
* Chapter 6. Solvation Dynamics in Dipolar Liquids
* 6.1 Introduction
* 6.2 Physical Concepts and Measurement
* 6.2.1 Measuring Ultrafast, Sub-100 fs Decay
* 6.3 Phenomenological Theories: Continuum Model Descriptions
* 6.3.1 Homogeneous Dielectric Models
* 6.3.2 Inhomogeneous Dielectric Models
* 6.3.3 Dynamic Exchange Model
* 6.4 Experimental Results: A Chronological Overview
* 6.4.1 Discovery of Multi-exponential Solvation Dynamics: Phase-I
(1980-1990)
* 6.4.2 Discovery of Sub-ps Ultrafast Solvation Dynamics: Phase-II
(1990-2000)
* 6.4.3 Solvation Dynamics in Complex Systems: Phase III (2000 - )
* 6.5 Microscopic Theories
* 6.5.1 Molecular Hydrodynamics Description
* 6.5.2 Polarization and Dielectric Relaxation of Pure Liquid
* 6.5.2.1 Effects of Translational Diffusion in Solvation Dynamics
* 6.6 Simple Idealized Models
* 6.6.1 Overdamped Solvation: Brownian Dipolar Lattice
* 6.6.2 Underdamped Solvation: Stockmayer Liquid
* 6.7 Solvation Dynamics in Water, Acetonitrile and Methanol Revisited
* 6.7.1 The Sub 100 fs Ultrafast Component: Microscopic Origin
* 6.8 Effects of Solvation on Chemical Processes in the Solution Phase
* 6.8.1 Limiting Ionic Conductivity of Electrolyte Solutions: Control
of a Slow Phenomenon by Ultrafast Dynamics
* 6.8.2 Effects of Ultrafast Solvation in Electron Transfer Reactions
* 6.8.3 Non-equilibrium Solvation Effects in Chemical Reaction
* 6.8.3.1 Strong Solvent Forces
* 6.8.3.2 Weak Solvent Forces
* 6.9 Solvation Dynamics in Several Related Systems
* 6.9.1 Solvation in Aqueous Electrolyte Solutions
* 6.9.2 Dynamics of Electron Solvation
* 6.9.3 Solvation Dynamics in Super-Critical Fluids
* 6.9.4 Nonpolar Solvation Dynamics
* 6.10 Computer Simulation Studies: Simple and Complex Systems
* Chapter 7. Activated Barrier Crossing Dynamics in Liquids
* 7.1 Introduction
* 7.2 Microscopic Aspects
* 7.2.1 Stochastic Models: Understanding from Eigenvalue Analysis
* 7.2.2 Validity of a Rate Law Description: Role of Macroscopic
Fluctuations
* 7.2.3 Time Correlation Function Approach: Separation of Transient
Behavior from Rate Law
* 7.3 Transition State Theory
* 7.4 Frictional Effects on Barrier Crossing Rate in Solution: Kramers'
Theory
* 7.4.1 Low Friction Limit
* 7.4.2 Limitations of Kramers' Theory
* 7.4.3 Comparison of Kramers' Theory with Experiments
* 7.4.4 Comparison of Kramers' Theory with Computer Simulations
* 7.5 Memory Effects in Chemical Reactions: Grote-Hynes Generalization
of Kramers' Theory
* 7.5.1 Frequency Dependence of Friction: General Aspects
* 7.5.1.1 Frequency Dependent Friction from Hydrodynamics
* 7.5.1.2 Frequency Dependent Friction from Mode Coupling Theory
* 7.5.2 Comparison of Grote-Hynes Theory with Experiments and Computer
Simulations
* 7.6 Variational Transition State Theory
* 7.7 Multidimensional Reaction Surface
* 7.7.1 Multidimensional Kramers' Theory
* 7.8 Transition Path Sampling
* 7.9 Quantum Transition State Theory
* Appendix
* Chapter 8. Barrierless Reactions in Solutions
* 8.1 Introduction
* 8.2 Standard Models of Barrierless Reactions
* 8.2.1 Exactly Solvable Models for Photochemical Reactions
* 8.2.1.1 Oster-Nishijima Model
* 8.2.1.2 Staircase Model
* 8.2.1.3 Pinhole Sink Model
* 8.2.2 Approximate Solutions for Realistic Models
* 8.2.2.1 Delta Function Sink
* 8.2.2.2 Gaussian Sink
* 8.3 Inertial Effects in Barrierless Reactions: Viscosity Turnover of
Rate
* 8.4 Memory Effects in Barrierless Reactions
* 8.5 Main Features of Barrierless Chemical Reactions
* 8.5.1 Excitation Wavelength Dependence
* 8.5.2 Negative Activation Energy
* 8.6 Multidimensional Potential Energy Surface
* 8.7 Analysis of Experimental Results
* 8.7.1 Photoisomerization and Ground State Potential Energy Surface
* 8.7.2 Decay Dynamics of Rhodopsin and Isorhodopsin
* 8.7.3 Conflicting Crystal Violet Isomerization Mechanism
* Chapter 9. Dynamical disorder, Geometric Bottlenecks and Diffusion
Controlled Bimolecular Reactions
* 9.1 Introduction
* 9.2 Passage through Geometric Bottlenecks
* 9.2.1 Diffusion in a Two Dimensional Periodic Channel
* 9.2.2 Diffusion in a Random Lorentz Gas
* 9.3 Dynamical Disorder
* 9.4 Diffusion over a Rugged Energy Landscape
* 9.5 Diffusion Controlled Bimolecular Reactions
* Chapter 10. Electron Transfer Reactions
* 10.1 Introduction
* 10.2 Classification of Electron Transfer Reactions
* 10.2.1 Classification of Electron Transfer Reactions Based on Ligand
Participation
* 10.2.2 Classification Based on Interactions between Reactant and
Product Potential Energy Surfaces
* 10.3 Marcus Theory
* 10.3.1 Reaction Coordinate
* 10.3.2 Free Energy Surfaces: Force Constant of Polarization
Fluctuation
* 10.3.3 Derivation of The Electron Transfer Reaction Rate
* 10.3.4 Experimental Verification Of Marcus Theory
* 10.4 Dynamical Solvent Effects on Electron Transfer Reactions (One
Dimensional Descriptions)
* 10.5 Role of Vibrational Modes in Weakening Solvent Dependence
* 10.5.1 Role of Classical Intramolecular Vibrational Modes:
Sumi-Marcus Theory
* 10.5.2 Role of High-Frequency Vibration Modes
* 10.5.3 Hybrid Model of Electron Transfer Reactions: Crossover from
Solvent to Vibrational Control
* 10.6 Theoretical Formulation of Multi-Dimensional Electron Transfer
* 10.7 Effects of Ultrafast Solvation on Electron Transfer Reactions
* 10.7.1 Absence of Significant Dynamic Solvent Effects on ETR in
Water, Acetonitrile and Methanol
* Appendix
* Chapter 11. Fõrster Resonance Energy Transfer
* 11.1 Introduction
* 11.2 A Brief Historical Perspective
* 11.3 Derivation of Förster Expression
* 11.3.1 Emission (or, Fluorescence) Spectrum
* 11.3.2 Absorption Spectrum
* 11.3.3 The Final Expression of Forster
* 11.4 Applications of Förster Theory in Chemistry, Biology and
Material Science
* 11.4.1 FRET Based Glucose Sensor
* 11.4.2 FRET and Macromolecular Dynamics
* 11.4.3 FRET and Single Molecule Spectroscopy
* 11.4.4 FRET and Conjugated Polymers
* 11.5 Beyond Förster Formalism
* 11.5.1 Orientation Factor
* 11.5.2 Point Dipole Approximation
* 11.5.3 Optically Dark States
* Chapter 12. Vibrational Energy Relaxation
* 12.1 Introduction
* 12.2 Isolated Binary Collision (IBC) Model
* 12.3 Landau-Teller Expression: The Classical Limit
* 12.4 Weak Coupling Model: Time Correlation Function Representation of
Transition Probability
* 12.5 Vibrational Relaxation at High Frequency: Quantum Effects
* 12.6 Experimental Studies of Vibrational Energy Relaxation
* 12.7 Computer Simulation Studies of Vibrational Energy Relaxation
* 12.7.1 Vibrational Energy Relaxation of Water
* 12.7.2 Vibrational Energy Relaxation in Liquid Oxygen and Nitrogen
* 12.8 Interference Effects on Vibrational Energy Relaxation on a Three
Level Systems: Breakdown of the Rate Equation Description
* 12.9 Vibrational Life Time Dynamics in Supercritical Fluids
* Chapter 13. Vibrational Phase Relaxation
* 13.1 Introduction
* 13.2 Kubo-Oxtoby Theory of Vibrational Lineshapes
* 13.3 Homogeneous vs. Inhomogeneous Linewidths
* 13.4 Relative Role of Attractive and Repulsive Forces
* 13.5 Vibration-Rotation Coupling
* 13.6 Experimental Results of Vibrational Phase Relaxation
* 13.6.1 Semi-Quantitative Aspects of Dephasing Rates in Solution
* 13.6.2 Sub-Quadratic Quantum Number Dependence
* 13.7 Vibrational Dephasing Near Gas-Liquid Critical Point
* 13.8 Multidimensional IR Spectroscopy
* Chapter 14. Epilogue