Gas Phase Metal Reactions (eBook)

Front Cover 1
Gas-Phase Metal Reactions 4
Copyright Page 5
Table of Contents 8
Preface 6
Chapter 1. Introduction and Overview 12
Abstract 12
1. OBJECTIVES, ORGANIZATION, AND PERSPECTIVE 12
2. REACTIONS OF NEUTRAL SPECIES 13
3. MAINLY REACTIONS INVOLVING IONIC AND EXCITED SPECIES 17
4. REACTION SYSTEMS INVOLVING CLUSTERS OR COMPETITION FROM GAS-SURFACE REACTIONS 20
REFERENCES 22
Chapter 2. Chemical Kinetics and Dynamics of the Mesospheric Sodium Nightglow 26
Abstract 26
1. INTRODUCTION 26
2. BACKGROUND ON SODIUM NIGHTGLOW KINETICS 27
3. SODIUM MONOXIDE FLOW TUBE CHEMICAL KINETICS 29
4. ELECTRONIC STATE SPECIFIC PRODUCTION OF NaO 32
5. ORBITAL CORRELATION ANALYSIS OF THE NaO + O 
35 
6. SUMMARY 36
7. ACKNOWLEDGEMENTS 36
8. REFERENCES 36
Chapter 3. A Comparison between the Oxidation Reactions of 
40 
Abstract 40
1. INTRODUCTION 40
2. EXPERIMENTAL TECHNIQUE 43
3. REACTIONS WITH N2O 48
4. REACTIONS WITH O2 58
5. ACKNOWLEDGMENTS 64
6. REFERENCES 64
Chapter 4. Kinetics of the Molecular Oxygen Reactions with 
68 
Abstract 68
1. INTRODUCTION 68
2. RECOMBINATION REACTION OF SODIUM ATOMS (32S) WITH MOLECULAR OXYGEN 69
3. RECOMBINATION REACTION OF COPPER ATOMS (42S) WITH MOLECULAR OXYGEN 73
4. RECOMBINATION REACTION OF MAGNESIUM ATOMS (31 
76 
Acknowledgement 81
References 81
Chapter 5. Kinetic Studies of Boron and Aluminum Species 84
Abstract 84
1. INTRODUCTION 84
2. EXPERIMENTAL 87
3. RESULTS AND DISCUSSION 90
4. SUMMARY 100
5. ACKNOWLEDGEMENTS 100
6. REFERENCES 100
Chapter 6. Homogeneous Kinetics of Metal Species over Wide Temperature Ranges: Techniques, Measurements, and Correlations 104
Abstract 104
1. INTRODUCTION 104
2. EXPERIMENTAL 106
3. SOME RESULTS 113
4. ACTIVATION BARRIER RELATIONSHIPS 119
APPENDIX A: PROCEDURES FOR THE HTP TECHNIQUE 126
ACKNOWLEDGEMENTS: 129
INFERENCES 129
Chapter 7. Reactions of Group III Metal Atom with Ethylene and Carbon Dioxide Molecules: A Matrix Isolation Study 132
Abstract 132
1. INTRODUCTION 132
2. EXPERIMENTAL 133
3. RESULTS 134
4. DISCUSSION 145
5 . CONCLUSIONS 154
ACKNOWLEDGMENTS. 156
REFERENCES 156
Chapter 8. Reactions of Boron and Aluminum Atoms with Small Molecules 158
Abstract 158
1. INTRODUCTION 158
2. THEORETICAL APPROACH 159
3. THEORETICAL PREDICTIONS OF STRUCTURES AND VIBRATIONAL FREQUENCIES 161
4. THERMOCHEMICAL ANALYSIS 173
5. KINETIC ANALYSIS 178
6. CONCLUSIONS 186
7. ACKNOWLEDGMENTS 186
Chapter 9. Ab Initio MO Calculations of the Thermochemistry of BX, A1X, OBX and OA1X (X = 0, F, C1) 
190 
Abstract 190
1. INTRODUCTION 190
2. METHOD 191
3. DISCUSSION 194
4. CONCLUSIONS 197
5. ACKNOWLEDGEMENTS 197
6. REFERENCES 197
Chapter 10. Reactive Collisions of AI, Mg, C and Si a 
200 
Abstract 200
1. INTRODUCTION 200
2. EXPERIMENTAL 204
3. ALUMINIUM ATOM REACTIONS22-23 
204 
4. MAGNESIUM ATOM REACTIONS29 212
5. CARBON ATOM REACTIONS33-34-35 216
6. SILICON ATOM REACTIONS 222
7. REFERENCES 223
Chapter 11. Cooperative Effects in Ligand Binding to Metal 
 
226 
Abstract 226
1. Introduction 226
2. AI(CO)2 and Ga(CO)2 229
3. Be(CO)2 and Be2(CO)4 232
4. Be(C2H4)(CO)n, n=0-2 233
5. Conclusions 235
6. Acknowledgments 235
7. References 236
Chapter 12. Association Reactions of Transition Metal Atoms 
238 
Abstract 238
1. INTRODUCTION 238
2. EXPERIMENTAL METHODS 238
3. BINDING ENERGIES OF 1:1 COMPLEXES 243
4. REACTIONS OF Cr, Fe, Ni AND Cu ATOMS 248
5. SUMMARY AND OUTLOOK 259
APPENDIX 260
Acknowledgement 261
REFERENCES 262
Chapter 13. Reactions of Gas Phase Transition Metal Atoms with Small Hydrocarbons 264
Abstract 264
1. INTRODUCTION 264
2. OVERVIEW OF ELECTRONIC STRUCTURE 265
3. M+ + HYDROCARBON REACTIONS 266
4. M2+ + HYDROCARBON REACTIONS 273
5. M + HYDROCARBON REACTIONS 276
6. SUMMARY AND PROGNOSIS 284
ACKNOWLEDGMENTS 285
REFERENCES 285
Chapter 14. The Bonding in Metal Ion Systems with Multiple Ligands 288
Abstract 288
1. INTRODUCTION 288
2. METHODS 289
3. RESULTS AND DISCUSSION 289
4. CONCLUSIONS 309
Acknowledgments 309
References 309
Chapter 15. Comparison of Main Group and Transition Metal Ion Chemistry 312
Abstract 312
1. INTRODUCTION 312
2. EXPERIMENTAL TECHNIQUE 313
3. STATISTICAL BEHAVIOR 314
4. IMPULSIVE BEHAVIOR 317
5. DIRECT BEHAVIOR 321
6. REACTIONS OF B+ AND Al+ 
325 
7. CONCLUSIONS 325
Chapter 16. Reaction Dynamics of Ground State and Electronically Excited Barium Atoms 330
Abstract 330
1. INTRODUCTION 330
2. EXPERIMENTAL 335
3. REACTIONS INVOLVING LONG-RANGE ELECTRON TRANSFER 336
4. REACTIONS INVOLVING CLOSE COLLISIONS 347
5. CONCLUSIONS 353
6. ACKNOWLEDGEMENTS 354
7. REFERENCES 354
Chapter 17. Effects of Electronic Excitation and Dimerization of 
360 
Abstract 360
1. INTRODUCTION 360
2- EXPERIMENTAL METHODS 361
3. OXIDATION REACTIONS OF GROUP 2 ATOMS 362
4. OXIDATION AND HALOGENATION REACTIONS OF GROUP 14 366
5. GROUP 15 REACTIONS WITH F2 368
6. SUMMARY 372
7. REFERENCES 372
Chapter 18. State-to-State Dynamics for the Reactions of 
374 
Abstract 374
1. INTRODUCTION 374
2. EXPERIMENTAL METHODS 381
3. EXPERIMENTAL RESULTS FOR Cu + Cl2 383
4. DISCUSSION 395
5. CONCLUSIONS 401
6. ACKNOWLEDGMENTS 401
7. REFERENCES 401
Chapter 19. The Interactions of Metal Atoms with Xe, CH4 and H2: Half-Collision Studies 404
Abstract 404
I. INTRODUCTION 405
II. SINGLET-TO-TRIPLET ENERGY TRANSFER. 407
III. INTRAMULTIPLET ENERGY TRANSFER 426
ACKNOWLEDGMENTS 442
REFERENCES 442
Chapter 20. Harpooning Reactions of Excited Rare Gas Atoms 446
Abstract 446
1. INTRODUCTION 446
2. EXPERIMENT 450
3. RESULTS 452
4. THE HARPOON REACTION 459
5. DISCUSSION 467
6. CONCLUSIONS 474
7. ACKNOWLEDGEMENTS 475
8. REFERENCES 475
Chapter 21. Studies of Some Gas-Phase Metal Oxidation Reactions 
478 
ABSTRACT 478
INTRODUCTION 478
CONCLUDING REMARKS 499
ACKNOWLEDGEMENTS 500
REFERENCES 500
Chapter 22. Metal Ion Chemistry in Flames 504
Abstract 504
1. INTRODUCTION 504
2. EXPERIMENTAL 508
3. ALKALI METALS - GROUP 1A 510
4. ALKALINE EARTH METALS - GROUP 2A (2) 515
5. GROUP 3A (13) METALS 519
6. GROUP 4A (14) METALS 522
7. TRANSITION METALS - GROUPS 3B-8B, IB, 2B (3-12) 526
8. METALLIC NEGATIVE IONS - GROUP 6B (6) 532
9. CONCLUSIONS 533
REFERENCES 535
Chapter 23. The Flame Chemistry of Alkali and Alkaline Earth Metals 540
Abstract 540
1. INTRODUCTION 540
2. KINETIC DESOUPTIONS 543
3. ALKAU/HYDRCXÎEN/OXYGEN SYSTEMS 545
4 ALKALINE EARTH/PIYDROGEN/OXYGEN SYSTEMS 552
5. INTERACTIONS WITH SULFUR COMPOUNDS 557
6. ALKAU/HALOGEN INTERACTIONS 561
7. ALKALINE EARTH/HALOGEN INTERACTIONS 562
8. INTERACTIONS WITH BORON COMPOUNDS 564
9. FORMATION OF CYANIDES 565
10. INTERACTIONS WITH PHOSPHORUS COMPOUNDS 567
11. INTERACTIONS WITH OTHER METALS 569
12. ION/NEUTRAL MOLECULE INTERACTIONS 571
13. CONCLUSIONS 573
14. REFERENCES 574
Chapter 24. Toward the Modeling of the Oxidation of Small 
584 
ABSTRACT 584
INTRODUCTION 584
NATURE OF METAL AND METALLOID MOLECULE SOURCES 586
AN EVALUATION OF THE BOND ENERGY AND LOW-LYING STATES OF THE BiF MOLECULE-EXTENSION TO ADDITIONAL GROUP 15 HALIDES 587
A CONTINUOUS VISIBLE CHEMICAL LASER AMPLIFIER FROM A METAL CLUSTER OXIDATION REACTION 597
OXIDATION IN MORE COMPLEX METAL AND METALLOID CLUSTER SYSTEMS 602
ACKNOWLEDGEMENT 610
REFERENCES 611
Chapter 25. Oxidation Reactions of Metal and Semi-Metal Cluster Ions 616
Abstract 616
1. INTRODUCTION 616
2. EXPERIMENTAL ARRANGEMENT 617
3. CARBON 617
4. BORON 622
5. ALUMINUM 627
6. CONCLUSIONS 630
Acknowledgements 630
7. REFERENCES 630
Chapter 26. Competition B 
632 
Abstract 632
1. INTRODUCTION 632
2. REACTION ZONE MODEL 634
3.RESULTS AND DISCUSSIONS 642
4. CONCLUDING REMARKS 650
ACKNOWLEDGEMENTS 651
5. REFERENCES 652
Chapter 27. Kinetics of High Temperature, Hydrocarbon 
654 
Abstract 654
1. INTRODUCTION 654
2. GAS PHASE BORON COMBUSTION KINETICS 655
3. GAS SURFACE REACTIONS 660
4. SUMMARY 667
5. ACKNOWLEDGEMENTS 670
6. REFERENCES 670
Chapter 28. Reactions of Metal Species in Dry Etching and Chemical Vapor Deposition 672
Abstract 672
1. INTRODUCTION 672
2. REACTIONS OF MEIMi SPECIES IN PLASMA-BASED ERY ETCHING TECHNIQUES 673
3. MEEAL REACTIONS IN CVD 682
4. SUMMARY 688
ACKNOWLEDGEMENTS 689
REFERENCES 689