Dynamics of Ion-Molecule Complexes (eBook)

William L Hase (Herausgeber)

eBook Download: PDF

2016 | 1. Auflage
329 Seiten
Elsevier Science (Verlag)
9781483283623 (ISBN)

Infos

Advances in Classical Trajectory Methods, Volume 2: Dynamics of Ion-Molecule Complexes is a seven-chapter text that covers the considerable advances in the experimental and theoretical aspects of ion-molecular complexes, with particular emphasis on the dynamics and kinetics of their formation and ensuing unimolecular dissociation. This text also considers the development and testing of theoretical models for these formation and decomposition processes. The opening chapters discuss photoelectron photoion coincidence, ion cyclotron resonance, and crossed molecular beam studies of metastable ion-molecule complexes formed in ion-molecule collisions. These experimental studies involve comparisons with the predictions of statistical models, such as the Rice-Ramsperger-Kassel-Marcus and phase space theories, and comparisons with the reaction dynamics predicted by classical trajectory calculations. The succeeding chapter describes the double-well model for ion-molecular reactions taking place on a potential energy surface with a central barrier that separates two potential energy minima. These topics are followed by reviews of the quantum chemical calculation and reaction path Hamiltonian analysis of SN2 reactions, the transition state theory for ion-dipole and ion-quadrupole capture, and the capture and dynamical models for ion-molecule association to form a complex. The remaining chapters consider the temperature dependence of ion-molecule reactions, which proceed on a surface with many potential energy minima, specifically the ability to establish asymptotic limits for the reaction efficiency dependent upon the number of potential minima and the above relative probabilities. This book is of great value to experimental and theoretical chemists and physicists.

Inhalt

Front Cover 1
Dynamics of Ion–Molecule Complexes 4
Copyright Page 5
Table of Contents 6
LIST OF CONTRIBUTORS 8
PREFACE 10
CHAPTER 1. LONG-LIVED ION COMPLEXES 12
I. INTRODUCTION 12
II. METASTABLE IONS AND THE STATISTICAL THEORY OF DISSOCIATION 14
III. ANGULAR MOMENTUM 17
IV. EXPERIMENTAL METHODS FOR RATE MEASUREMENTS 25
V. COMPETITIVE REACTIONS VIA TIGHT AND LOOSE TRANSITION STATES 27
VI. ISOMERIZATION VERSUS DISSOCIATION 33
VII. DISSOCIATION OF ION-DIPOLE COMPLEXES 42
VIII. TUNNELING IN UNIMOLECULAR DISSOCIATIONS 44
IX. FUTURE DIRECTIONS 49
ACKNOWLEDGMENTS 50
REFERENCES 50
CHAPTER 2. CROSSED BEAM STUDIES OF ION-MOLECULE REACTIONS: COLLISIONS AND COMPLEXES 54
I. INTRODUCTION 54
II. EXPERIMENTAL 56
III. REPRESENTATIVE COLLISION COMPLEX SYSTEMS 58
III. CONCLUDING REMARKS 101
ACKNOWLEDGMENTS 102
REFERENCES 102
CHAPTER 3. THE DOUBLE-WELL MODEL FOR ION-MOLECULE REACTIONS 106
I. INTRODUCTION 106
II. ORIGIN AND DESCRIPTION OF THE MODEL 107
III. EXPERIMENTAL CONSEQUENCES OF THE MODEL 108
IV. THEORETICAL SUPPORT FOR THE MODEL 115
V. USES OF THE MODEL 117
VI. DIFFICULTIES WITH THE MODEL 120
VII. OUTLOOK 123
ACKNOWLEDGMENT 123
REFERENCES 123
CHAPTER 4. COMPLEX FORMATION AND DIRECT COLLISION DYNAMICS IN GAS-PHASE NUCLEOPHILIC SUBSTITUTION REACTIONS 126
I. INTRODUCTION 127
II. RATE CONSTANT CALCULATIONS FOR NONSTATISTICAL CHEMICAL REACTIONS 130
III. COLLINEAR (1D) MODEL FOR THE GAS-PHASE NUCLEOPHILIC SUBSTITUTION REACTIONS 133
IV. THERMAL RATE CONSTANT CALCULATIONS AND DYNAMIC FACTORS INFLUENCING THE REACTION EFFICIENCY 146
V. REACTION PATH HAMILTONIAN ANALYSIS AND THE VALIDITY OF THE COLLINEAR REACTION MODEL 149
VI. CONCLUSION 152
APPENDIX 154
ACKNOWLEDGMENT 154
REFERENCES 155
CHAPTER 5. THEORETICAL STUDIES OF ION-MOLECULE CAPTURE AND COMPLEX FORMATION DYNAMICS IN MOLECULAR COLLISIONS 158
I. INTRODUCTION 159
II. ION-MOLECULE CAPTURE 160
III. QUANTUM EFFECTS ON ION-DIPOLE CAPTURE 176
IV. THE CONCEPT OF A COLLISION COMPLEX: STUDIES OF ATOM-MOLECULE COLLISIONS 194
V. SYNTHESIS 214
REFERENCES 217
CHAPTER 6. TRANSITION STATE THEORY OF FAST CHARGE-TRANSFER REACTIONS IN ION-DIPOLE AND ION-QUADRUPOLE SYSTEMS 220
I. INTRODUCTION 221
II. GENERAL REMARKS CONCERNING THE TRANSITION STATE THEORY 222
III. REVIEW OF THE EARLIER USES OF TST TO DESCRIBE THE FORMATION OF POLARIZATION COMPLEXES 226
IV. TST FOR FAST CHARGE TRANSFER 228
V. CLASSICAL TST FOR ION-LINEAR DIPOLE REACTION 229
VI. QUANTUM TST FOR ION-LINEAR DIPOLE REACTION 240
VII. CLASSICAL TST FOR ION-LINEAR QUADRUPOLE REACTION 247
VIII. QUANTUM TST FOR ION-LINEAR QUADRUPOLE REACTION 254
IX. SUMMARY 260
REFERENCES 262
CHAPTER 7. RATE CONSTANTS AND THEIR TEMPERATURE DEPENDENCES: A KINETIC DESCRIPTION USING SIMPLE MODEL POTENTIAL-ENERGY SURFACES 266
ABSTRACT 267
I. HISTORICAL BACKGROUND 269
II. SIMPLE POTENTIAL-ENERGY SURFACES AND THEIR CORRELATION WITH REACTANT ELECTRONIC STRUCTURE 271
III. TEMPERATURE DEPENDENCE OF RATE CONSTANTS: CORRELATION WITH POTENTIAL-ENERGY SURFACE 279
IV. POTENTIAL-ENERGY SURFACES WITH MANY BASINS 290
V. SUMMARY 299
APPENDIX 300
ACKNOWLEDGMENTS 301
REFERENCES 301
INDEX 306

Produkt-Details

• Erscheint lt. Verlag: 29.7.2016
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Mechanik
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Quantenphysik
• Themenwelt: Technik
• ISBN-13: 9781483283623 / 9781483283623