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THÔNG TIN TÀI LIỆU
Cấu trúc
Cover
Half-title
Title
Copyright
Dedication
Contents
Preface
Acknowledgments
Chapter 1 Understanding chemical reactions at the molecular level
1.1 What is molecular reaction dynamics?
1.1.1 Much of chemistry is local: from the elementary act to complex systems
1.2 An example: energy disposal in an exoergic chemical reaction
1.2.1 Distribution of products’ energy states
1.2.2 Simple view of products’ energy disposal: the spectator
1.2.3 Products’ angular distribution
1.2.4 From specific energy disposal to the mode-selective control of chemical reactions
1.2.5 The experiment
1.2.6 Launching the system in the transition state region: the first steps toward control
1.2.7 The steric requirements of chemical reactions
1.2.7.1 Abstraction vs. insertion
1.2.8 The time scales of the chemical change
1.2.9 Reaction dynamics in solution and on surfaces
*1.2.9.1 Chaos and spatiotemporal pattern formation
1.2.10 The road ahead
Appendix: Units
Problems
Notes
Chapter 2 Molecular collisions
2.1 Molecules have a finite size
2.1.1 Direct determination of the mean free path by a scattering experiment
2.1.2 Quantitative analysis of the scattering experiment
*2.1.3 The mean free path and the probability of a collision
2.1.4 The collision cross-section
2.1.5 The rate of molecular collisions
2.1.6 Molecules as hard spheres
2.1.7 Realistic short-range repulsion
2.1.8 Toward realistic interatomic potentials
2.1.9 Simplistic approach to long-range interatomic and intermolecular forces
2.1.10 Sources of interaction potentials
*2.1.10.1 Deviations from ideal gas behavior and intermolecular forces
*2.1.10.2 Potential curves from beam scattering
2.1.11 On to collision dynamics
On to collision dynamics
2.2 The approach motion of molecules
2.2.1 The classical trajectory and the impact parameter
2.2.2 The centrifugal barrier and the effective potential
2.2.2.1 The distance of closest approach
2.2.3 On the centrifugal force
2.2.4 The micro view of the cross-section
*2.2.4.1 On controlling the impact parameter
2.2.5 Qualitative examination of the deflection function
2.2.6 Rainbow scattering and the quantum mechanical interference of different trajectories
*2.2.7 The center-of-mass system
*2.2.7.1 Kinematics in the center-of-mass system
*2.2.7.2 Kinematics in velocity space: the Newton diagram
Problems
Notes
Chapter 3 Introduction to reactive molecular collisions
3.1 The Rate and cross-section of chemical reactions
3.1.1 The thermal reaction rate constant
3.1.2 The reaction cross-section – a macroscopic view
3.1.2.1 The energy threshold of reaction
3.1.2.2 Translational energy requirements of chemical reactions On the basis of the translational energy requirements of chemical reactions we can thus make the following…
3.1.2.3 The temperature dependence of the reaction rate constant
3.1.2.4 The Tolman interpretation of the activation energy: the reactive reactants
3.A Appendix: Reaction rate under non-equilibrium conditions
3.2 Two-body microscopic dynamics of reactive collisions
3.2.1 The opacity function
3.2.2 The microscopic view of the reaction cross-section
3.2.3 A simple opacity function
3.2.4 The harpoon mechanism
3.2.4.1 A modern variation on an old theme: excimer lasers
3.2.4.2 Hardness and electronegativity
*3.2.4.3 Dynamics in condensed phases: a simple application of curve crossing
3.2.5 The centrifugal barrier to reaction
3.2.5.1 Computing the capture cross-section for reactions with no energy threshold
3.2.6 Reactions with an energy threshold
3.2.7 The steric factor
*3.2.7.1 A simple model of steric requirements: the cone of acceptance
*3.2.7.2 The cone of acceptance can depend on energy and on the impact parameter
3.2.7.3 Steric hindrance
3.2.8 Two aspects of scattering
3.B Appendix: Dynamics in strong laser fields – a curve-crossing picture
Problems
Notes
Chapter 4 Scattering as a probe of collision dynamics
4.1 Classical scattering of structureless particles
4.1.1 Conservation of angular momentum
4.1.2 The angle of deflection
4.1.3 The deflection function for hard spheres and for realistic potentials
4.1.4 Angular distribution in the c.m. system: the differential cross-section
4.2 Elastic scattering as a probe of the interaction potential
4.2.1 Scattering as a probe of the potential
4.2.2 The angle of deflection as a measure of the potential
*4.2.2.1. The energy and impact parameter dependence of the angle of deflection
4.2.3 The quantitative route from the potential to the deflection function
4.2.4 The total cross-section and the glory effect
4.2.5 Rainbow scattering as a probe of the potential well
4.3 Elements of quantal scattering theory
4.3.1 Essential quantum mechanics: the superposition principle
4.3.2 The quantum mechanical approach to elastic scattering
4.3.3 The scattering amplitude
4.3.4 The cross-section and the random phase approximation
4.3.5 Time delay and resonances
4.3.6 Low-energy collisions: classical orbiting and quantal resonances
4.4 Angular distribution for reactive molecular collisions
4.4.1 The angular distribution as a probe of direct vs. compound collisions
4.4.2 Direct reactions: forward vs. backward scattering
4.4.3 Scattering in direct reactions
*4.4.4 Information gained from non-reactive scattering
4.4.5 Summary
4.4.6 On to polyatomics
Problems
Notes
Chapter 5 Introduction to polyatomic dynamics
5.0.1 The Born–Oppenheimer separation: a caveat
5.1 Potential energy functions and chemical reactions
5.1.1 Potential energy surfaces
5.1.2 The reaction path
*5.1.2.1 Input from spectroscopy of large-amplitude motions
5.1.3 Semi-empirical potential surfaces
5.1.3.1 The conical intersection for the LEP(S) potential
5.1.4 The Evans–Polanyi model
5.1.5 The cone of acceptance: qualitative considerations
*5.1.5.1 From structure to reactivity: on orbital steering
5.1.6 The steric effect: the polar map representation
5.1.7 Stable and unstable polyatomics
5.1.8 Collision-induced dissociation
5.1.9 On to energy requirements and energy disposal of chemical reactions
5.2 The classical trajectory approach to reaction dynamics
5.2.1 From the potential surface to the dynamics
5.2.2 The need for averaging trajectory results
*5.2.2.1 Chaos and longer time evolution of the quasi-classical trajectory method
5.A Appendix: Monte Carlo sampling
*5.A.1 An example of Monte Carlo sampling
5.3 Energy and dynamics of the chemical change
5.3.1 Energy disposal in direct exoergic reactions
5.3.2 Energy requirements for reactions with a barrier
5.3.3 Direct vs. compound collisions
5.3.3.1 Complex mode trajectories and unimolecular reactions
5.3.4 Stereodynamics
5.3.5 On to the specificity of energy disposal and selectivity of energy requirements
5.B Appendix: Mass-weighted coordinate systems
Problems
Notes
Chapter 6 Structural considerations in the calculation of reaction rates
6.1 Transition state theory: the rate of barrier crossing
6.1.1 The point of no return and the transition state
6.1.2 The statistical condition
6.1.3 Computing the rate for direct reactions
6.1.4 From k(E) to k(T)
*6.1.4.1 Transition state theory and the steric factor
*6.1.4.2 Variational transition state theory
6.A Appendix: Density of states and partition functions
6.2 RRKM theory and the rate of unimolecular reactions
6.2.1 Unimolecular reactions: the Lindemann and the RRKM hypotheses
6.2.2 The (RRKM) dissociation rate of an energy-rich polyatomic molecule
6.2.2.1 Reactions in the bulk
*6.2.2.2 Vibrational state counting: a simplified treatment
*6.2.2.3 The vibrational quasi-continuum
6.2.2.4 Do energy-rich polyatomic molecules behave statistically?
6.2.3 The reaction rate for a complex-forming collision
6.2.3.1 A case study: ion–molecule reactions
6.2.4 Toward molecular machines
6.3 Resolving final states and populations
6.3.1 Scattering in velocity space: the Newton sphere
6.3.1.1 Flux–velocity maps: qualitative aspects
6.B Appendix: The quantitative representation of flux contour maps
*6.B.1 Reduced distributions: translational energy release and angular distribution
6.4 Characterization of energy disposal and energy requirements of chemical reactions
6.4.1 The prior distribution
*6.4.1.1 The prior flux distribution
*6.4.1.2 Products’ internal state distribution in the prior limit
6.4.2 Surprisal analysis
*6.4.2.1 The distribution of maximal entropy
6.4.3 Measure of selectivity in energy requirements of chemical reactions
6.4.4 There are deviations from statistics
6.4.5 Phase space theory
6.4.6 Up, up and away
Problems
Notes
Chapter 7 Photoselective chemistry: access to the transition state region
7.0.1 The Franck–Condon principle
7.0.2 Beyond the Born–Oppenheimer approximation
7.0.3 Radiationless transitions
7.A Appendix: The picket-fence model
7.1 Laser photoexcitation and photodetection of diatomic molecules
7.1.1 The discrete vibrational energy levels of diatomic molecules
7.1.2 Electronic excitation
7.1.2.1 Angular distribution in photodissociation
7.1.2.2 The photochemistry of molecular oxygen in the atmosphere
*7.1.2.3 Interference of exit channels
7.1.3 Photodetection
7.1.3.1 Imaging and translational spectroscopy
7.1.3.2 Doppler spectroscopy
7.1.3.3 Laser-induced fluorescence
7.2 Photodissociation dynamics
7.2.1 Direct and indirect processes
7.2.2 Unimolecular dissociation
7.2.3 Access to the transition state region: vibrationally mediated photodissociation
7.2.4 Mode-selective chemistry
7.2.4.1 Unimolecular dissociation of van der Waals clusters
7.2.5 Multiphoton dissociation
7.2.5.1 Infrared multiphoton dissociation
7.2.5.2 Multiphoton ionization/dissociation
7.2.6 On to quantum control and the time domain
7.3 Bimolecular spectroscopy
7.3.1 Collision-induced light absorption
7.3.2 Pressure broadening of spectral lines
7.3.3 Emission in half collisions
7.3.4 Spectroscopy of elastic collisions
7.3.5 Spectroscopy of the transition state and laser-assisted collisions
7.4Quantum control
7.4.1 Strong field control
Problems
Notes
Chapter 8 Chemistry in real time
*8.0.1The coherent state – a wave-packet
8.1 Watching the breaking and making of chemical bonds
8.1.1 Photoinitiated bond-breaking
8.1.1.1 Bond-breaking occurs along more than one dimension
8.1.1.2 Coherence
8.1.2 Bimolecular collisions
8.2 Chemical transformations
8.2.1 Concerted vs. sequential bond forming
8.3 Control of chemical reactions with ultrashort pulses
8.3.1 Control by pump and probe
Problems
Notes
Chapter 9 State-changing collisions: molecular energy transfer
9.0.1 Equilibrium and disequilibrium
9.0.2 A hierarchy of relaxation rates
9.0.3 The HF chemical laser
9.1 Vibrational energy transfer
9.1.1 V–V' processes in diatomics
9.1.2 V–V processes in polyatomics
9.1.2.1 The CO2 laser
9.1.3 Energy-rich polyatomics
9.2 Understanding the essentials of energy transfer
9.2.1 Two extremes of vibrational energy transfer
9.2.2 The adiabaticity parameter
9.2.2.1 Rotational energy transfer
9.2.2.2 Adiabatic behavior
9.2.3 The exponential gap
9.2.4 Light as a bridge of the exponential gap
9.2.5 Propensity rules for energy transfer
9.2.6 Detailed balance
9.3 Electronic energy transfer
9.3.1 Non-adiabatic processes
9.3.2 Curve crossing
9.3.2.1 Diabatic vs. adiabatic
*9.3.3 The adiabaticity parameter for curve crossing
*9.3.4 The Landau–Zener transition probability
*9.3.5 The localized crossing range
*9.3.6 Donor–acceptor systems and photoinduced charge separation
*9.3.7 From photons to perception
Problems
Notes
Chapter 10 Stereodynamics
10.0.1 The steric factor and early history of stereodynamics
10.1 Controlling reagent approach geometry
10.1.1 Preparing oriented molecules in electric fields
10.1.2 Preparing aligned molecules with polarized radiation
10.1.3 Electronic orbital control
10.2 Analyzing product polarization
10.2.1 Conservation of angular momentum
10.2.2 Kinematic models
*10.2.3 The degree of orientation and alignment
10.2.4 Inelastic collisions
10.2.5 Surface scattering
10.2.6 Bimolecular reactions
10.2.6.1 PHOTOLOC
10.2.6.2 Peripheral dynamics
10.3 Vector correlations
10.3.1 v, v' correlation
10.3.1.1 The collision complex
10.3.1.2 Photodissociation
Problems
Notes
Chapter 11 Dynamics in the condensed phase
11.0.1 Many facets of the solvent
11.1 Solvation
11.1.1 Electrostatic models for solvation
*11.1.1.1 The Born solvation model
11.1.2 Electron transfer reactions
11.1.3 Dynamics of solvation
11.1.3.1 Cage effect
11.1.3.1.1 Diffusion control
11.1.3.2 Caging dynamics
11.1.3.3 Caging dynamics in clusters
11.1.4 Vibrational relaxation
11.2 Barrier-crossing dynamics
11.2.1 Potential of mean force
*11.2.1.1 Evaluating the mean force
11.2.1.2 From gas phase to solution
11.2.2 Isomerization
*11.2.2.1 Toy model for barrier crossing
11.3 Interfaces
11.3.1 The gas–liquid interface
11.3.2 The liquid–liquid interface
11.3.3 Fuel cells
11.4 Understanding chemical reactivity in solution
11.4.1 The reaction series
11.4.2 The unified approach
11.4.3 Recapitulations
Problems
Notes
Chapter 12 Dynamics of gas–surface interactions and reactions
12.0.1 A clean surface?
12.0.2 The reconstructed surface
12.0.3 The electronically active surface
12.1 Surface scattering
12.1.1 Inelastic scattering
12.1.1.1 Trapping at the surface
12.1.2 Collision-induced surface processes
12.2 Dynamics on surfaces
12.2.1 Dissociative adsorption
12.2.2 Heterogeneous chemical reactivity
12.2.3 Dynamics of gas–surface reactions
12.2.4 Laser-induced processes
12.3 Chaos and pattern formation: spatiotemporal aspects of surface reactivity