Advances in Quantum Chemistry (eBook)

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2009 | 1. Auflage
348 Seiten
Elsevier Science (Verlag)
978-0-08-088785-2 (ISBN)

Infos

Advances in Quantum Chemistry presents surveys of current developments in this rapidly developing field. With invited reviews written by leading international researchers, each presenting new results, it provides a single vehicle for following progress in this interdisciplinary area.
* Publishes articles, invited reviews and proceedings of major international conferences and workshops
* Written by leading international researchers in quantum and theoretical chemistry
* Highlights important interdisciplinary developments

Inhalt

Front Cover 1
Advances in Quantum Chemistry Volume 56 4
Copyright Page 5
Table of Contents 6
Preface 10
Contributors 12
Chapter 1. Multireference and Spin–Orbit Calculations on Photodissociations of Hydrocarbon Halides 14
1. Introduction 15
2. Computational Methods 16
3. Photodissociation of Aryl Halides 17
3.1. Monohalobenzenes and heavy atomic effect 17
3.2. Bromobenzene, dibromobenzene, and 1,3,5-tribromobenzene and bromine substituent effect 20
3.3. Photon energy effect on the dissociation channels: chlorobenzene dissociation at 193, 248, and 266 nm 21
3.4. Chlorobenzene, chlorotoluene, and methyl substituent and rotation effects 24
4. Photodissociation Processes of Halomethane 27
4.1. Bromoiodomethane (CH2BrI) 27
4.2. Dichloromethane (CH2Cl2) 32
4.3. Diiodomethane (CH2I2) 34
5. Conclusions 38
Acknowledgments 39
References 39
Chapter 2. Quantum Linear Superposition Theory for Chemical Processes: A Generalized Electronic Diabatic Approach 44
1. Introduction 45
2. Basic Quantum Mechanics and Chemical Processes 46
3. Basic Space–Time-Projected Quantum Formalism 53
3.1. Time-projected formalism 53
3.2. Configuration space basis 54
4. Abstract Quantum Formalism 58
4.1. Schrödinger equation in configuration space 59
4.2. Electronuclear configuration space 60
4.3. Hamiltonians 61
4.4. Abstract generalized electronic diabatic model 64
5. Semiclassical Models 68
5.1. Class I models: a-BO and GED schemes 70
5.2. Class II models 72
6. The AO Ansatz: Nodal Patterns 75
6.1. Nodal patterns 76
6.2. Mapping a chemical reaction D-PES 83
6.3. Generalized many-state reactivity framework 85
7. Algorithms: Comments and Proposal 88
7.1. Nodal patterns algorithm 89
7.2. Diabatic (ghost) orbital algorithm 90
7.3. Standard BO and diabatization procedures 93
7.4. How far from exact representations are GED-BO schemes? 95
7.5. The Jahn–Teller effect and linear superposition principle 97
8. Discussion 98
Acknowledgments 100
Appendix 101
References 105
Chapter 3. Exact Signal–Noise Separation by Froissart Doublets in Fast Padé Transform for Magnetic Resonance Spectroscopy 108
1. Introduction 109
2. Rational Response Function to Generic External Perturbations 110
3. The Exact Solution for the General Harmonic Inversion Problem 112
4. Delayed Time Series 113
5. Delayed Green Function 115
6. The Key Prior Knowledge: Internal Structure of Time Signals 117
7. The Rutishauser Quotient–Difference Recursive Algorithm 120
8. The Gordon Product–Difference Recursive Algorithm 124
9. Delayed Lanczos Continued Fractions 130
10. Delayed Padé–Lanczos Approximant 137
11. Fast Padé Transform FPT(–) Outside the Unit Circle 140
12. Fast Padé Transform FPT(+) Inside the Unit Circle 145
13. Signal–Noise Separation via Froissart Doublets (Pole–Zero Cancellations) 150
14. Critical Importance of Poles and Zeros in Generic Spectra 151
15. Spectral Representations via Padé Poles and Zeros: pFPT(±) and zFPT(±) 152
16. Padé Canonical Spectra 153
17. Signal–Noise Separation: Exclusive Reliance upon Resonant Frequencies 154
18. Model Reduction Problem via Padé Canonical Spectra 155
19. Denoising Froissart Filter 156
20. Signal–Noise Separation: Exclusive Reliance upon Resonant Amplitudes 156
21. Padé Partial Fraction Spectra 160
22. Model Reduction Problem via Padé Partial Fraction Spectra 161
23. Disentangling Genuine from Spurious Resonances 162
24. Results 163
25. Conclusion 187
Acknowledgment 190
References 190
Chapter 4. Reflections on Formal Density Functional Theory 194
1. Introduction 195
2. The Hohenberg–Kohn Construction of an Exact Density Functional and Its Extensions 196
2.1. Review of the Hohenberg–Kohn construction of an exact density functional 197
2.2. Nonuniversal density-like functionals satisfying a variational principle 202
2.3. Functionals of the Hartree–Fock density 205
2.4. Nonuniversal functionals of the density containing an explicit external potential-dependent part 207
3. Generalizations of The Kohn–Sham Density Functional Formulation: Inclusion of Exact Exchange 208
3.1. Review of Kohn–Sham theory as a constrained search formulation of the kinetic energy functional 209
3.2. Application of the Kohn–Sham formalism to the exact Hartree–Fock energy 213
3.3. Kohn–Sham exchange theory 216
3.4. Generalizations of the Kohn–Sham exchange formalism to an exact density functional theory 218
3.5. Further generalizations to orbital-dependent Kohn–Sham formulations 219
4. Concluding Remarks 221
Acknowledgments 228
References 228
Chapter 5. Multiple, Localized, and Delocalized/Conjugated Bonds in the Orbital Communication Theory of Molecular Systems 230
1. Introduction 230
2. Entropic Descriptors of Molecular Information Channels in Orbital Resolution 233
3. Illustrative Application to Localized Bonds in Hydrides 239
4. Atom Promotion in Hydrides 243
5. One- and Two-Electron Approaches to Conjugated p-Bonds in Hydrocarbons 246
6. Model Multiple Bonds 251
7. p-Bond Conjugation 254
8. Concluding Remarks 259
References 261
Chapter 6. Quantum Mechanical Methods for Loss-Excitation and Loss-Ionization in Fast Ion–Atom Collisions 264
1. Introduction 265
2. Simultaneous Projectile Ionization and Target Excitation and/or Ionization 266
3. Adiabatic Hypothesis for Resonance Massey Peak 269
4. Electron Loss Processes and Stopping Powers of Heavy Ions 272
5. Channel Scattering States and Perturbations 273
6. The T-Matrix for Short-Range Interactions 275
6.1. First Born approximation 275
7. The T-Matrix for Long-Range Interactions 276
7.1. Boundary-corrected first Born approximation 278
8. Defining, Exact Sum Over all the Target Final States 281
8.1. The mass approximation for heavy particle collisions 282
9. Practical, Exact Sum Over Dominant Target True Final States 285
10. Acceleration of Convergence for Final States 287
11. Closure Approximation 292
12. Corrected Closure Approximation 298
13. Comparison Between Theories and Experiments 301
13.1. Testing the CB1-4B method 305
13.2. Testing the ACB1-4B method 319
13.3. Testing the CCA method 324
14. Conclusion 328
Acknowledgment 330
References 330
Index 336

Produkt-Details

• Erscheint lt. Verlag: 14.3.2009
• Mitarbeit: Herausgeber (Serie): Erkki J. Brandas, John R. Sabin
• Sprache: englisch
• Themenwelt: Sachbuch/Ratgeber
• Themenwelt: Naturwissenschaften ► Biologie
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Atom- / Kern- / Molekularphysik
• Themenwelt: Technik
• ISBN-10: 0-08-088785-6 / 0080887856
• ISBN-13: 978-0-08-088785-2 / 9780080887852