Spectra and Dynamics of Diatomic Molecules (eBook)

Revised and Enlarged Edition

Robert W. Field, Helene Lefebvre-Brion (Autoren)

eBook Download: EPUB

2004 | 1. Auflage
786 Seiten
Elsevier Science (Verlag)
978-0-08-051750-6 (ISBN)

Infos

This book is written for graduate students just beginning research, for theorists curious about what experimentalists actually can and do measure, and for experimentalists bewildered by theory. It is a guide for potential users of spectroscopic data, and uses language and concepts that bridge the frequency-and time-domain spectroscopic communities.

Key topics, concepts, and techniques include: the assignment of simple spectra, basic experimental techniques, definition of Born-Oppenheimer and angular momentum basis sets and the associated spectroscopic energy level patterns (Hund's cases), construction of effective Hamiltonian matrices to represent both spectra and dynamics, terms neglected in the Born-Oppenheimer approximation (situations intermediate between Hund's cases, spectroscopic perturbations), nonlinear least squares fitting, calculation and interpretation of coupling terms, semi-classical (WKB) approximation, transition intensities and interference effects, direct photofragmentation (dissociation and ionization) and indirect photofragmentation (predissociation and autoionization) processes, visualization of intramolecular dynamics, quantum beats and wavepackets, treatment of decaying quasi-eigenstates using a complex Heff model, and concluding with some examples of polyatomic molecule dynamics.

Students will discover that there is a fascinating world of cause-and-effect localized dynamics concealed beyond the reduction of spectra to archival molecular constants and the exact ab initio computation of molecular properties. Professional spectroscopists, kinetics, ab initio theorists will appreciate the practical, simplified-model, and rigorous theoretical approaches discussed in this book.

Key Features:

&bull, A fundamental reference for all spectra of small, gas-phase molecules.

&bull, It is the most up-to-date and comprehensive book on the electronic spectroscopy and dynamics of diatomic molecules.

&bull, The authors pioneered the development of many of the experimental methods, concepts, models, and computational schemes described in this book.

- A fundamental reference for all spectra of small, gas-phase molecules.
- Emphasizes the role of perturbations in understanding the dynamics of isolated molecules.
- Includes new applications of interest to researchers in all areas of chemistry and materials science.

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This book is written for graduate students just beginning research, for theorists curious about what experimentalists actually can and do measure, and for experimentalists bewildered by theory. It is a guide for potential users of spectroscopic data, and uses language and concepts that bridge the frequency-and time-domain spectroscopic communities. Key topics, concepts, and techniques include: the assignment of simple spectra, basic experimental techniques, definition of Born-Oppenheimer and angular momentum basis sets and the associated spectroscopic energy level patterns (Hund's cases), construction of effective Hamiltonian matrices to represent both spectra and dynamics, terms neglected in the Born-Oppenheimer approximation (situations intermediate between Hund's cases, spectroscopic perturbations), nonlinear least squares fitting, calculation and interpretation of coupling terms, semi-classical (WKB) approximation, transition intensities and interference effects, direct photofragmentation (dissociation and ionization) and indirect photofragmentation (predissociation and autoionization) processes, visualization of intramolecular dynamics, quantum beats and wavepackets, treatment of decaying quasi-eigenstates using a complex Heff model, and concluding with some examples of polyatomic molecule dynamics. Students will discover that there is a fascinating world of cause-and-effect localized dynamics concealed beyond the reduction of spectra to archival molecular constants and the exact ab initio computation of molecular properties. Professional spectroscopists, kinetics, ab initio theorists will appreciate the practical, simplified-model, and rigorous theoretical approaches discussed in this book. - A fundamental reference for all spectra of small, gas-phase molecules- It is the most up-to-date and comprehensive book on the electronic spectroscopy and dynamics of diatomic molecules- The authors pioneered the development of many of the experimental methods, concepts, models, and computational schemes described in this book

Inhalt

Cover 1
Contents 6
Chapter 1. Simple Spectra and Standard Experimental Techniques 32
1.1 Rotation-Vibration-Electronic Spectra of Diatomic Molecules 33
1.2 Experimental Techniques of Diatomic Molecule Spectroscopy 52
1.3 References 86
Chapter 2. Basic Models 92
2.1 What Is a Perturbation? 93
2.2 Structural Models 100
2.3 Elementary Properties of Angular Momenta in Diatomic Molecules 103
2.4 Estimation of Parameters in a Model Hamiltonian 114
2.5 Data Compilations 115
2.6 References 116
Chapter 3. Terms Neglected in the Born-Oppenheimer Approximation 118
3.1 The Born-Oppenheimer Approximation 120
3.2 Basis Functions 130
3.3 Electrostatic Perturbations 192
3.4 Spin Part of the Hamiltonian 211
3.5 Rotational Perturbations 241
3.6 References 258
Chapter 4. Methods of Deperturbation 264
4.1 Variational Calculations 265
4.2 The Van Vleck Transformation and Effective Hamiltonians 268
4.3 Approximate Solutions 274
4.4 Exact Solutions 279
4.5 Typical Examples of Fitted Perturbations 298
4.6 References 303
Chapter 5. Interpretation of the Perturbation Matrix Elements 306
5.1 Calculation of the Vibrational Factor 309
5.2 Order of Magnitude of Electrostatic Perturbation Parameters:Interactions Between Valence and Rydberg States of the Same Symmetry 338
5.3 Order of Magnitude of Spin Parameters 346
5.4 Magnitudes of Rotational Perturbation Parameters 356
5.5 Pure Precession Approximation 358
5.6 R-Dependence of the Spin Interaction Parameters 364
5.7 Beyond the Single-Configuration Approximation 371
5.8 Identification and Location of Metastable States by Perturbation Effects 372
5.9 References 373
Chapter 6. Transition Intensities and Special Effects 378
6.1 Intensity Factors 379
6.2 Intensity Borrowing 399
6.3 Interference Effects 409
6.4 Forbidden Transitions Intensity Borrowing by Mixing with a Remote Perturber
6.5 Special Effects 446
6.6 References 491
Chapter 7. Photodissociation Dynamics 500
7.1 Photofragmentation 501
7.2 Direct Dissociation 502
7.3 Introduction to Predissociation 524
7.4 Experimental Aspects of Predissociation 526
7.5 Theoretical Expressions for Widths and Level Shifts 536
7.6 The Vibrational Factor 541
7.7 Mulliken's Classification of Predissociations 545
7.8 The Electronic Interaction Strength 549
7.9 Fano Lineshape 553
7.10 Isotope Effects 557
7.11 Examples of Predissociation 559
7.12 Case of Intermediate Coupling Strength 566
7.13 Indirect (Accidental) Predissociation and Interference Effects 569
7.14 Some Recipes for Interpretation 574
7.15 References 576
Chapter 8. Photoionization Dynamics 582
8.1 Direct Ionization 583
8.2 Experimental Aspects of Autoionization 595
8.3 The Nature of Autoionized States 599
8.4 Autoionization Widths 600
8.5 Rotational Autoionization 603
8.6 Vibrational Autoionization 607
8.7 Spin-Orbit Autoionization 612
8.8 Electronic (or Electrostatic) Autoionization 617
8.9 Validity of the Approximations 619
8.10 Influence of Autoionization on ZEKE Peak Intensities 622
8.11 Photoelectron Angular Distribution, Photoion Alignment, and Spin Polarization 626
8.12 Competition between Autoionization and Predissociation 635
8.13 Coherent Control of Photofragmentation Product Branching Ratios 640
8.14 References 646
Chapter 9. Dynamics 652
9.1 Dynamical Concepts, Tools, and Terminology 653
9.2 From Quantum Beats to Wavepackets 687
9.3 Relaxation into a Quasi-Continuum: A Tool for Dimensionality Reduction 702
9.4 Beyond the Spectra and Dynamics of Diatomic Molecules 714
9.5 References 767
Index 772

Produkt-Details

• Erscheint lt. Verlag: 28.4.2004
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Analytische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Atom- / Kern- / Molekularphysik
• Themenwelt: Technik
• ISBN-10: 0-08-051750-1 / 0080517501
• ISBN-13: 978-0-08-051750-6 / 9780080517506