Springer Atomic, Optical, and Plasma Physics

By: Tetsuo Miyazaki (Editor)

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Hardcover | 13 January 2004

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332 Pages

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23.5 x 15.88 x 2.54

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Atom tunneling phenomena are a new paradigm in the science of materials. This book provides a wealth of interesting information about atom tunneling phenomena in physics, chemistry and biology. Topics include the theory of atom tunneling reactions, conclusive evidence and controlling factors for such reactions in solid hydrogen, tunneling dislocation motion, coherent tunneling diffusion, the production of interstellar molecules and semiconductors using tunneling reactions, the effect of atom tunneling on molecular structure and crystalline structure, the suppression of mutation and cancer by an atom tunneling reaction of vitamin C, and atom tunneling reactions of vitamin E and of enzymes. This book provides graduate students and nonspecialist readers with fascinating insights into the world of atom tunneling phenomena.

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Introduction	p. 1
Atom Tunneling Phenomena	p. 1
Aim of the Book	p. 4
Outline of the Book	p. 7
References	p. 11
Atom Tunneling in Physics
Theory of Atom Tunneling Reactions in the Gas Phase	p. 15
Introduction	p. 15
What is Tunneling in Chemical Reactions?	p. 16
Quantum Mechanical Methods for Calculating Rate Constants	p. 18
Low Temperature Behavior of Rate Constants: Wigner Threshold Law	p. 20
Effect of van der Waals Interactions on Tunneling Reactions	p. 21
H + H₂ Tunneling Reaction in Solid Phase: Application of Gas-Phase Models	p. 24
Tunneling in the F + H₂, D₂, and HD Reactions	p. 26
Conclusion and Future Development	p. 28
References	p. 29
Theory of Atom Tunneling Reactions in the Solid Phase	p. 33
Introduction	p. 33
Description of Low Temperature Chemical Reactions	p. 36
Experimental Data on H-Atom Tunneling and Fitting by One Dimensional Model	p. 42
Effect of Promotive Modes on the Rate Constant of Atom Tunneling	p. 43
Relaxation Processes	p. 44
Time of Tunneling Transition	p. 44
Double Adiabatic Approximation	p. 45
Modified Theory of Radiationless Transitions	p. 46
Comparison of Theory with Experimental Data	p. 48
Mechanisms of Temperature and Pressure Dependencies of the Rate Constant	p. 49
Role of Medium Reorganization in D-Transfer in an Irradiated HD Crystal	p. 50
H-atom Tunneling in the Fluorene-Acridine System	p. 52
Conclusion and Future Development	p. 54
References	p. 55
Atom Tunneling Reactions in Quantum Solid Hydrogen	p. 59
Introduction. Classical Reactions and Tunneling Reactions	p. 59
Temperature Dependence	p. 60
Isotope Effect	p. 62
ESR Measurement at Very Low Temperature	p. 63
Conclusive Evidence for Atom Tunneling Reactions	p. 64
Temperature Independence	p. 65
Large Isotope Effect	p. 66
Comparison of Experimental Rate Constants with Theoretical Values	p. 68
Controlling Factors of Classical Reactions	p. 70
Controlling Factors of Tunneling Reactions	p. 70
Effect of Deformation of Crystalline Structure	p. 70
Anomalous Temperature Effect on the Decay of <$>{\rm H}_2^-<$> Anions	p. 74
Effect of Disorder and Energy Dissipation	p. 77
Inverse Secondary Isotope Effect of Methyl Radical Reactions	p. 85
Fascinating Quantum Properties of Solid Hydrogen	p. 86
Conclusion and Future Development	p. 87
References	p. 88
Atom Tunneling Phenomena in Quantum Solid and Liquid Helium	p. 91
Introduction. Quantum Nature of Helium Atoms	p. 91
Nuclear Magnetic Ordering of Solid ³He Arising from Tunneling of Atoms	p. 92
Quantum Nucleation in Superfluid Helium by Tunneling	p. 98
Tunneling Motion of Dislocation Lines in Solid ³He	p. 103
Conclusion and Future Development	p. 108
References	p. 109
Quantum Tunneling Diffusion	p. 111
Introduction	p. 111
Quantum Tunneling Diffusion of Positive Muons and Muonium	p. 112
Effect of Disorder and Superconductivity	p. 115
Muonium in a Bloch State	p. 117
Conclusion and Future Development	p. 123
References	p. 123
Atom Tunneling in Chemistry
Fascinating Aspects of Tunneling Reactions in Organic Substances	p. 127
Introduction	p. 127
Selective Tunneling Reaction in Alkane Mixtures by H Atoms	p. 128
Formation of H Atoms in Radiolysis of Alkane	p. 128
Evidence for Tunneling Reaction	p. 131
Selectivity in Tunneling Reaction	p. 132
Local Motion and Selective Tunneling Reaction	p. 135
Selective Tunneling Reaction in the Same Alkane by H Atoms	p. 138
Instability of Molecules. Tunneling Elimination of H₂ Molecule from Alkane Cation	p. 140
Instability of Molecules. Tunneling cis-trans Isomerization of Formic Acid	p. 144
Conclusion and Future Development	p. 145
References	p. 145
Tunneling Insertion Reaction of Carbenes	p. 147
Introduction	p. 147
Dicoordinate Carbon Intermediate-Carbenes	p. 147
Carbenes Have Two-Electronic States Singlet and Triplet Multiplicities	p. 148
Singlet and Triplet States Show Different Reaction Patterns	p. 149
How to Generate a Carbene	p. 151
Reactions of Arylcarbenes with Alkenes at 77 K	p. 152
Reactions of Arylcarbenes with Alcohols at 77 K	p. 155
Tunneling C-H Insertion from Triplet Carbenes at Low Temperature	p. 157
Why Can Only Triplets Find a Tunneling Pathway?	p. 160
Tunneling Reactions of Carbene Having Intramolecular Reaction Channels	p. 161
Tunneling in Intramolecular Reactions	p. 164
Tunneling Reaction at Elevated Temperatures	p. 166
Conclusion and Future Development	p. 170
References	p. 171
Production of Interstellar Molecules and Amorphous Semiconductors by Atom Tunneling Reaction	p. 173
Introduction	p. 173
Method	p. 175
Laboratory Simulation of H-atom Tunneling Reactions in Interstellar Ices	p. 177
Gas-Grain Processes for the Formation of NH₃, CH₄, and H₂O	p. 178
Formation of Formaldehyde by the Tunneling Reaction of H with Solid CO at 10 K	p. 182
Tunneling Reactions of H Atoms with Solid C₂H₂, C₂H₄, and C₂H₆	p. 184
Tunneling Reactions of D Atoms with C₂H₂, C₂H₄ and C₂H₆: Isotope Effect	p. 189
Negative Temperature Dependence of H-Atom Tunneling Reactions	p. 190
Formation of Amorphous Semiconductor by H-Atom Tunneling Reactions	p. 193
Conclusion and Future Development	p. 197
References	p. 198
Atom Tunneling and Molecular Structure	p. 201
Introduction	p. 201
Experimental Methods	p. 201
Proton Tunneling in Molecules and Complexes	p. 206
Proton Tunneling in Molecules	p. 206
Proton Tunneling in Complexes	p. 219
Conclusion and Future Development	p. 227
References	p. 228
Atom Tunneling in Biology
Atom Tunneling and Crystalline Structure	p. 233
Introduction	p. 233
General Considerations on X-Ray and Neutron Diffraction, Crystal Structure and Phase Transitions	p. 234
Proton Tunneling in Hydrogen-Bonded Crystals	p. 237
Tunneling Energy Levels of Ammonium Ions in Ammonium Hexachlorometallates: Global and Local Rotation and Tunneling	p. 245
Delocalization of H (D) Atoms. Structure of (NH₄)₂PtCl₆, (NH₄)₂SnCl₆ and (ND₄)₂SnCl₆ by Neutron Diffraction	p. 251
Other Compounds Possessing Strong Isotope-Dependent Properties	p. 257
Conclusion and Future Development	p. 258
References	p. 258
Atom Tunneling in Biology
Atom Tunneling Reaction of Vitamin C in Suppression of Mutation	p. 263
Introduction	p. 263
Tunneling Reaction at Room Temperature	p. 263
How to Study Tunneling Reactions in Biological Systems	p. 265
Long-Lived Radicals in ¿-Irradiated Cells	p. 267
Discovery of Long-Lived Radicals and Reactions with Vitamin C	p. 267
Why Do Reactive Radicals Survive for a Long Time?	p. 269
Assignment of Long-Lived Radicals	p. 272
Reaction of Long-Lived Radicals with Vitamin C	p. 275
Biological Effects of Tunneling Reaction of Long-Lived Radicals with Vitamin C	p. 277
Tunneling Reaction of Long-Lived Radicals with Vitamin C	p. 280
Conclusion and Future Development	p. 282
References	p. 283
Atom Tunneling Reaction of Vitamin E in Antioxidant, Prooxidant and Regeneration Reactions	p. 285
Introduction	p. 285
Tunneling Antioxidant Reaction of Vitamin E	p. 289
Prooxidant Reaction of Vitamin E	p. 295
Tunneling Regeneration Reaction of Vitamin E	p. 298
Conclusion and Future Development	p. 301
References	p. 302
Index	p. 305
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Springer Atomic, Optical, and Plasma Physics

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