Verfügbarkeit: Molecular reaction dynamics and chemical reactivity

Molecular reaction dynamics and chemical reactivity:

Gespeichert in:

Bibliographische Detailangaben
Beteiligte Personen:	Levine, Raphael D. 1938- (VerfasserIn), Bernstein, Richard B. 1923-1990 (VerfasserIn)
Format:	Buch
Sprache:	Englisch
Veröffentlicht:	New York, NY [u.a.] Oxford Univ. Press 1987
Schlagwörter:	Dynamique moléculaire Réactions chimiques - Mécanismes Chemical reaction, Conditions and laws of Molecular Biology Molecular dynamics Theorie Molekulardynamik Chemische Reaktion Reaktionskinetik Molekülphysik Reaktionsdynamik
Links:	http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=000502798&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA
Umfang:	XII, 535 S. graph. Darst.
ISBN:	0195041399 0195053958

Internformat

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Datensatz im Suchindex

DE-BY-TUM_call_number	0290 B.17.C.69 0290 B.17.C.69a 0290 B.17.C.69b
DE-BY-TUM_katkey	86171
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adam_text	Molecular Reaction Dynamics and Chemical Reactivity Raphael D Levine The Hebrew University of Jerusalem Richard B Bernstein University of California, Los Angeles New York Oxford OXFORD UNIVERSITY PRESS Contents 1 Understanding molecular collisions 3 1 1 What is molecular dynamics? 3 1 2 An example: Infrared chemiluminescence 4 121 Distribution of products energy states 5 122 From population inversion to chemical lasers 6 1 3 Why molecular dynamics? 6 131 The pragmatic approach 7 132 Disequilibrium 7 133 The purist approach 9 14A simple model of energy partitioning 10 141 The spectator 10 142 Product angular distribution 11 143A quantitative detour 12 144 The reverse reaction 13 145 Lasers in molecular dynamics 14 1 5 The need to know 15 151 The size of molecules 17 152 Angular distribution of elastic and reactive scattering 17 153 Energy and chemical change 18 154 The practice of molecular reaction dynamics 18 155 Energy transfer collisions 19 156 Molecular reaction dynamics 20 Suggested Reading 21 List of Edited Volumes of Relevant Review Literature 21 2 Molecular collisions 26 2 1 Molecular collisions and free-path phenomena 26 211 The concept of molecular size 26 212 Transport phenomena 27 213 Direct determination of the mean free path: A simple scattering experiment 27 214 The collision cross section 29 215 The collision frequency 30 216 Molecules as rigid spheres 30 viii Contents 217 Realistic intermolecular potentials 32 218 The concept of molecular size 35 2 2 Dynamics of elastic molecular collisions 36 221 Elastic collisions of structureless particles 36 222 The center-of-mass system 37 223 The centrifugal energy 38 224 The impact parameter 39 225 Conservation of angular momentum; relation to impact parameter 41 226 The centrifugal barrier 43 227 The collision cross section 44 2 3 The reaction cross section 46 231 Definition of reaction cross section 47 232 The energy threshold for reaction 48 233 Trarislational energy requirements of chemical reactions 52 2 4 The reaction probability 52 241 The opacity function 52 242 Reaction cross section 53 243A simple opacity function 54 244 The steric factor 55 245 Reactive asymmetry 55 246 The centrifugal barrier to reaction 58 247 Cross sections for reactions without an energy barrier 59 248 Reactions with an energy threshold 59 249A simple model of steric requirements 61 Suggested Reading 64 3 Scattering as a probe of the collision dynamics 67 3 1 Elastic scattering as a probe of the interaction potential 68 311 The angular deflection 68 312 The deflection function 68 313 Angular distribution in the center-of-mass system 70 314 Scattering as a probe of the potential 73 315 From the potential to the deflection function 74 316 The differential cross section 76 317 The quantum mechanical approach to elastic scattering 78 318 The total cross section and the glory effect 83 319 Rainbow scattering as a probe of the potential well 86 3 1 10 Rainbows in inelastic scattering 87 Appendix 3A: Relation between scattering in the center-of-mass and laboratory systems 91 3 2 Intermolecular potentials from experiment and theory 94 321 Sources of interaction potentials 94 322 Potential curves from beam scattering 95 323 The intermolecular potential 98 324 Long-range intermolecular forces 102 3 3 Angular distribution in direct reactive collisions 104 331 Concept of a direct reactive collision 104 332 Angular distributions for direct reactions 107 333 Optical model approach to direct reactions 109 Contents ix 334 Nonreactive scattering 110 335 Angular distribution for rebound reactions 111 Suggested Reading 113 4 The polyatomic approach to chemical dynamics 117 4 1 Energy and chemical change 117 411 Energy partitioning 117 412 Energy consumption 120 4 2 Three-body potential energy functions and chemical reactions 122 421 Potential energy surfaces 122 422 The reaction path 125 423 Determining the potential energy surface 129 424 Semiempirical potential surfaces 132 425 Qualitative interpretations: The example of the harpoon mechanism 134 426 The steric factor: Qualitative and quantitative considerations 137 427 The steric effect: Polar map representation 142 428 Unimolecular reaction and collision-induced dissociation 143 4 3 The classical trajectory approach to reaction dynamics 148 431 From the potential surface to the dynamics 148 432 The need for averaging trajectory results 149 433 Energy disposal in exoergic reactions 151 434 Energy requirements for reactions with a barrier 155 435 Dynamics by classical trajectories 157 436 Direct versus compound collisions 160 437 Monte Carlo sampling 162 Appendix 4A: Mass-weighted coordinate systems 165 Appendix 4B: Role of angular momentum 169 Appendix 4C: Kinematic models 172 4 4 From microscopic dynamics to macroscopic kinetics 173 441 State-to-state rate constants 173 442 Sum over final states, average over initial states 175 443 Detailed balance 177 444 The thermal reaction rate constant 179 445 Activation energy and the reactive reactants 181 446 The configuration of no return 182 447 Evaluating the reaction rate 183 448 Activated complex theory for k(T) 187 449 The statistical approximation 191 4 4 10 Compound collisions: Unimolecular versus bimolecular rates 192 4 4 11 Photoselective chemistry 195 Suggested Reading 198 5 The practice of molecular reaction dynamics 207 5 1 The wish and the realization 207 511 Desiderata 207 5 2 Molecules, radiation, and laser interactions 210 521 Chemiluminescence 210 522 Chemical lasers 211 X Contents 523 Laser pump and laser probe experiments 215 524 Photofragmentation spectroscopy 218 525 Lasers as effectors and detectors of chemical change 225 Appendix 5A: Laser-induced fluorescence 229 5 3 Molecular and ion beam scattering 233 531 Crossed molecular beams 233 532 Ion-molecule reactions 236 Appendix 5B: Supersonic beams 243 5 4 The collisional method 247 541 Angular distribution of reaction products 247 542 Scattering in velocity space 248 543 Intensity contour maps: Qualitative aspects of flux-velocity distributions 253 544 Translational exoergicity and angular distributions 256 5 5 Surprisal 260 551 Measures of selectivity and specificity 260 552 Surprisal analysis of energy disposal 262 553 Surprisal analysis of energy requirements 267 554 The maximum entropy formalism 270 Appendix 5C: The prior distribution - 274 5 6 Quantum dynamics 276 561 Coupled channels 277 562 From the S matrix to the cross section 279 563 The classical path limit 281 564 The sudden approximation for fast collisions 284 565 Wave packets 285 566 Natural collision coordinates 287 567 Statistical dynamics 287 568 Concluding remarks 289 Suggested Reading 289 6 Molecular energy transfer 300 61A macroscopic description of energy transfer 300 611 Equilibrium and disequilibrium 300 612 The relaxation rate equations 301 613 The relaxation time 302 614 Overview of relaxation rates 303 615A hierachy of relaxation times 305 616 Laser-induced fluorescence spectroscopy 305 617 V-V processes in poly atomics 306 618 The COz laser 311 6 2 Simple models of energy transfer 312 621 Two extremes of vibrational energy transfer 312 622 The adiabaticity parameter 314 623 The exponential gap 316 624 Intermolecular potential for vibrational excitation 320 625 Vibrational energy transfer for the Landau-Teller model 322 626 Classical trajectories for the Landau-Teller model 324 627 Rotational energy transfer in the sudden limit 327 Contents xi 6 3 State-to-state inelastic collisions 331 631 State-to-state rate constants 332 632 Molecular beam studies of inelastic collisions 335 633 Angular distribution 337 6 4 Collisions of molecules with surfaces 338 641 Surface scattering 340 642 Inelastic atom-surface collisions 340 643 Experimental studies of molecule-surface scattering 344 6 5 Bimolecular spectroscopy 348 651 The importance of collisions 348 652 Collision-induced light absorption 349 653 Quasi-bound states and predissociation 351 654 Pressure broadening of spectral lines 353 655 Bimolecular emission spectroscopy 356 656 Laser-assisted collision processes 359 6 6 Electronic energy transfer 368 661 Collisions of electronically excited species 368 662 Quenching processes 369 663 The He-Ne laser 371 664 Radiationless transitions 373 665 Curve crossing 375 666 The adiabaticity parameter 376 667 The Landau-Zener transition probability 377 668 Angular distribution in the curve-crossing problem 378 669 Steric effects in collisions of electronically excited reagents 380 6 6 10 Back to chemistry 382 Appendix 6A: Stimulated emission, laser action, and molecular lasers 383 Suggested Reading 387 7 Reaction dynamics and chemical reactivity 396 71A case study of an elementary reaction 396 711 The F + H2 reaction 396 712 Early experiments: In the beginning 3 9 6 713A landmark: Crossed molecular beam study 397 714 Theoretical attacks on the dynamics 398 715 Definitive product state distributions at last! 401 716 Angular distribution of products and the resonances 407 7 2 Collision complexes: Their formation and decay 411 721A union of bimolecular-unimolecular concepts 411 722A simple model of the angular distribution 412 723 Qualitative criteria for complex formation: Structure and stability 417 724 Quantitative considerations: The available energy 421 725 The RRKM unimolecular reaction rate 426 726 Energy disposal and energy consumption in compound collisions 427 7 3 Multiphoton dissociation 429 731 Intramolecular vibrational energy redistribution 430 732 Infrared multiphoton dissociation 432 733 Molecular beam studies 436 xii Contents 734 Multiphoton ionization and fragmentation 440 Appendix 7A: Beyond RRKM/QET 443 7 4 Van der Waals molecules and clusters 444 741 Beams of molecular clusters 446 742 Spectroscopic and structural studies 448 743 Chemical reactivity of clusters 452 744 Reaction dynamics 454 7 5 Molecular dynamics of gas-surface reactions 459 751 Adsorption and desorption 460 752 Dissociative adsorption 463 753 Heterogeneous chemical reactivity 467 754 Dynamics of gas-surface reactions 469 755 Laser-induced processes 473 7 6 Stereospecific dynamics 473 761 Orientation and alignment of reactant molecules 476 762 Orbital control 483 763 Alignment of reaction products 484 764 Repulsive energy release 490 765 Photopolarization 490 7 7 New frontiers 495 771 Understanding chemical reactivity 496 772 Future directions 497 Suggested Reading 502 General Appendix 511 Subject Index 513 Author Index 525
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author	Levine, Raphael D. 1938- Bernstein, Richard B. 1923-1990
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spellingShingle	Levine, Raphael D. 1938- Bernstein, Richard B. 1923-1990 Molecular reaction dynamics and chemical reactivity Dynamique moléculaire Réactions chimiques - Mécanismes Chemical reaction, Conditions and laws of Molecular Biology Molecular dynamics Theorie (DE-588)4059787-8 gnd Molekulardynamik (DE-588)4170370-4 gnd Chemische Reaktion (DE-588)4009853-9 gnd Reaktionskinetik (DE-588)4048655-2 gnd Molekülphysik (DE-588)4039979-5 gnd Reaktionsdynamik (DE-588)4301792-7 gnd
subject_GND	(DE-588)4059787-8 (DE-588)4170370-4 (DE-588)4009853-9 (DE-588)4048655-2 (DE-588)4039979-5 (DE-588)4301792-7
title	Molecular reaction dynamics and chemical reactivity
title_auth	Molecular reaction dynamics and chemical reactivity
title_exact_search	Molecular reaction dynamics and chemical reactivity
title_full	Molecular reaction dynamics and chemical reactivity Raphael D. Levine ; Richard B. Bernstein
title_fullStr	Molecular reaction dynamics and chemical reactivity Raphael D. Levine ; Richard B. Bernstein
title_full_unstemmed	Molecular reaction dynamics and chemical reactivity Raphael D. Levine ; Richard B. Bernstein
title_short	Molecular reaction dynamics and chemical reactivity
title_sort	molecular reaction dynamics and chemical reactivity
topic	Dynamique moléculaire Réactions chimiques - Mécanismes Chemical reaction, Conditions and laws of Molecular Biology Molecular dynamics Theorie (DE-588)4059787-8 gnd Molekulardynamik (DE-588)4170370-4 gnd Chemische Reaktion (DE-588)4009853-9 gnd Reaktionskinetik (DE-588)4048655-2 gnd Molekülphysik (DE-588)4039979-5 gnd Reaktionsdynamik (DE-588)4301792-7 gnd
topic_facet	Dynamique moléculaire Réactions chimiques - Mécanismes Chemical reaction, Conditions and laws of Molecular Biology Molecular dynamics Theorie Molekulardynamik Chemische Reaktion Reaktionskinetik Molekülphysik Reaktionsdynamik
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work_keys_str_mv	AT levineraphaeld molecularreactiondynamicsandchemicalreactivity AT bernsteinrichardb molecularreactiondynamicsandchemicalreactivity

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