Molecular Collision Dynamics

ISBN-13: 9783642819452 / Angielski / Miękka / 2011 / 160 str.

J. M. Bowman

Opis

This monograph covers a broad spectrum of topics in the very broad field of gas phase molecular collision dynamics. The Introduction previews each of the four fol lowing topics and attempts to sew them together with a common thread. In addition, a brief review of quantum reactive scattering is given there along with some gen eral remarks which highlight the difficulties in doing quantum reactive scatter ing calculations. The chapters are all written by theoreticians who are, of course, experts in the subjects they have written about. Three chapters, the ones by Secrest, Schatz, and the one by Schinke and Bowman deal with non-reactive atom-molecule scattering. Col lectively, they describe nearly the full breadth of scattering methods in use to day, from fully quantum mechanical to semiclassical and quasiclassical. The chapter by Baer is the only one dealing with quantum reactive scattering with the additional complexity of the coupling of two potential energy surfaces. The one simplifying feature of the treatment is that the reaction is constrained to be collinear. Overall, this monograph is mainly a review of the recent advances in the field of molecular collision dynamics, with, however, a considerable amount of new material. It is hoped that workers and students in the field will find reading the mono graph both enlightening and enjoyable."

Spis treści

1. Introduction.- References.- 2. Inelastic Vibrational and Rotational Quantum Collisions.- 2.1 General Computational Techniques.- 2.1.1 The Scattering Equations.- 2.1.2 Boundary Conditions.- 2.1.3 Asymptotic Approximations.- 2.2 A Higher-Order Coupled States Approximation.- 2.2.1 The Phase in the Body Fixed Coordinate System.- 2.2.2 Correcting the Coupled States Approximation.- References.- 3. Quasiclassical Trajectory Studies of State to State Collisional Energy Transfer in Polyatomic Molecules.- 3.1 Background.- 3.2 Semiclassical Vibration-Rotation Motions of Polyatomic Molecules.- 3.2.1 Classical Molecular Hamiltonian.- 3.2.2 Rotational-Vibrational Partitioning.- 3.2.3 Vibrational Semiclassical Eigenstates: Classical Perturbation Theory.- 3.2.4 Rotational Motions and Eigenstates.- 3.3 Trajectory Studies of Polyatomic Molecule Collisions.- 3.3.1 Trajectory Initial Conditions.- 3.3.2 Trajectory Final Conditions.- 3.3.3 Assignment of Final Quantum States.- 3.4 Collisional Excitation in He + SO2.- 3.4.1 Details of Trajectory Calculations.- 3.4.2 Trajectory Results.- 3.5 Conclusion.- References.- 4. Rotational Rainbows in Atom-Diatom Scattering.- 4.1 Background.- 4.1.1 Experiment.- 4.1.2 Theory.- 4.1.3 Outline.- 4.2 Review of Rainbows in Isotropic Potential Scattering.- 4.3 Classical Limit of the IOS Approximation.- 4.3.1 Basic IOS Formulas.- 4.3.2 Classical Limit of (4.14) for j = 0.- 4.3.3 Uniform Approximation.- 4.3.4 Qualitative Behavior of Cross Sections.- 4.3.5 Relationship to Other Work.- 4.4 Numerical Examples.- 4.4.1 Homonuclear Case.- 4.4.2 Heteronuclear Case.- 4.5 Recent Experiments and Comparison with Theory.- 4.5.1 State-Unresolved Experiments.- 4.5.2 State-Resolved Experiments.- 4.6 Approximate Analytical Expressions for X(?,?),J(?,?) and the Rainbow Curve jR(?).- 4.6.1 Hard Shell Scattering.- 4.6.2 High Energy Approximation.- 4.7 Conclusion and Prognosis.- References.- 5. Quantum Mechanical Treatment of Electronic Transitions in Atom-Molecule Collisions.- 5.1 The General Approach.- 5.1.1 The Diabatic Representation.- 5.1.2 The Adiabatic Representation.- 5.1.3 The Adiabatic-Diabatic Transformation.- 5.1.4 The Adiabatic-Diabatic Transformation in Three Dimensions.- 5.2 Numerical Examples.- 5.2.1 Reactive Systems.- (a) The (H2 + H)+ System.- (b) The (Ar + H2)+ System.- (c) The Ba + N2O System.- (d) The F + H2 System.- 5.2.2 Nonreactive Systems.- 5.3 Electronic Nonadiabatic Processes Among Potential Curves.- 5.3.1 Reducing the Surface Crossing Problem to a Curve Crossing Problem.- 5.3.2 The Two-Curve Model.- 5.3.3 A Multi-Curve Crossing Model for Reactions.- (a) The Model.- (b) The Simplified Models.- 5.4 Electronic Nonadiabatic Processes in Strong Laser Fields.- 5.5 Summary and Conclusions.- References.