Atom Tunneling, Phenomena in Physics, Chemistry and Biology (Springer Series on Atomic, Optical, and Plasma Physics Vol.36) (2004. 375 p. w. 153 ill.)

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Atom Tunneling, Phenomena in Physics, Chemistry and Biology (Springer Series on Atomic, Optical, and Plasma Physics Vol.36) (2004. 375 p. w. 153 ill.)

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  • 製本 Hardcover:ハードカバー版/ページ数 375 p.
  • 商品コード 9783540015260

基本説明

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, and more.

Full Description


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.

Table of Contents

1. Introduction (T. Miyazaki)                      1  (14)
1.1 Atom Tunneling Phenomena 1 (3)
1.2 Aim of the Book 4 (3)
1.3 Outline of the Book 7 (4)
References 11 (4)
Part 1 Atom Tunneling in Physics
2 Theory of Atom Tunneling Reactions in the 15 (18)
Gas Phase (T. Takayanagi)
2.1 Introduction 15 (1)
2.2 What is Tunneling in Chemical 16 (2)
Reactions?
2.3 Quantum Mechanical Methods for 18 (2)
Calculating Rate Constants
2.4 Low Temperature Behavior of Rate 20 (1)
Constants: Wigner Threshold Law
2.5 Effect of van der Waals 21 (3)
Interactions on Tunneling Reactions
2.6 H + H2 Tunneling Reaction in Solid 24 (2)
Phase: Application of Gas-Phase Models
2.7 Tunneling in the F + H2, D2, and HD 26 (2)
Reactions
2.8 Conclusion and Future Development 28 (1)
References 29 (4)
3 Theory of Atom Tunneling Reactions in the 33 (26)
Solid Phase (L.I. Trakhtenberg)
3.1 Introduction 33 (3)
3.2 Description of Low Temperature 36 (6)
Chemical Reactions
3.3 Experimental Data on H-Atom 42 (1)
Tunneling and Fitting by One
Dimensional Model
3.4 Effect of Promotive Modes on the 43 (1)
Rate Constant of Atom Tunneling
3.4.1 Relaxation Processes 44 (1)
3.4.2 Time of Tunneling Transition 44 (1)
3.4.3 Double Adiabatic Approximation 45 (1)
3.4.4 Modified Theory of Radiationless 46 (2)
Transitions
3.4.5 Comparison of Theory with 48 (1)
Experimental Data
3.5 Mechanisms of Temperature and 49 (1)
Pressure Dependencies of the Rate
Constant
3.5.1 Role of Medium Reorganization in 50 (2)
D-Transfer in an Irradiated HD Crystal
3.5.2 H-atom Tunneling in the 52 (2)
Fluorene-Acridine System
3.6 Conclusion and Future Development 54 (1)
References 55 (4)
4 Atom Tunneling Reactions in Quantum Solid 59 (32)
Hydrogen (T. Miyazaki)
4.1 Introduction. Classical Reactions 59 (1)
and Tunneling Reactions
4.1.1 Temperature Dependence 60 (2)
4.1.2 Isotope Effect 62 (1)
4.2 ESR Measurement at Very Low 63 (1)
Temperature
4.3 Conclusive Evidence for Atom 64 (1)
Tunneling Reactions
4.3.1 Temperature Independence 65 (1)
4.3.2 Large Isotope Effect 66 (2)
4.3.3 Comparison of Experimental Rate 68 (2)
Constants with Theoretical Values
4.4 Controlling Factors of Classical 70 (1)
Reactions
4.5 Controlling Factors of Tunneling 70 (1)
Reactions
4.5.1 Effect of Deformation of 70 (4)
Crystalline Structure
4.5.2 Anomalous Temperature Effect on 74 (3)
the Decay of H2- Anions
4.5.3 Effect of Disorder and Energy 77 (8)
Dissipation
4.5.4 Inverse Secondary Isotope Effect 85 (1)
of Methyl Radical Reactions
4.6 Fascinating Quantum Properties of 86 (1)
Solid Hydrogen
4.7 Conclusion and Future Development 87 (1)
References 88 (3)
5 Atom Tunneling Phenomena in Quantum Solid 91 (20)
and Liquid Helium (Y. Miura)
5.1 Introduction. Quantum Nature of 91 (1)
Hellum Atoms
5.2 Nuclear Magnetic Ordering of Solid 92 (6)
3He Arising from Tunneling of Atoms
5.3 Quantum Nucleation in Superfluid 98 (5)
Helium by Tunneling
5.4 Tunneling Motion of Dislocation 103(5)
Lines in Solid 3He
5.5 Conclusion and Future Development 108(1)
References 109(2)
6 Quantum Tunneling Diffusion (R. Kadono) 111(16)
6.1 Introduction 111(1)
6.2 Quantum Tunneling Diffusion of 112(3)
Positive Muons and Muonium
6.3 Effect of Disorder and 115(2)
Superconductivity
6.4 Muonium in a Bloch State 117(6)
6.5 Conclusion and Future Development 123(1)
References 123(4)
Part 2 Atom Tunneling in Chemistry
7 Fascinating Aspects of Tunneling 127(20)
Reactions in Organic Substances (T.
Miyazaki)
7.1 Introduction 127(1)
7.2 Selective Tunneling Reaction in 128(1)
Alkane Mixtures by H Atoms
7.2.1 Formation of H Atoms in 128(3)
Radiolysis of Alkane
7.2.2 Evidence for Tunneling Reaction 131(1)
7.2.3 Selectivity in Tunneling Reaction 132(3)
7.2.4 Local Motion and Selective 135(3)
Tunneling Reaction
7.3 Selective Tunneling Reaction in the 138(2)
Same Alkane by H Atoms
7.4 Instability of Molecules. Tunneling 140(4)
Elimination of H2 Molecule from Alkane
Cation
7.5 Instability of Molecules. Tunneling 144(1)
cis-trans Isomerization of Formic Acid
7.6 Conclusion and Future Development 145(1)
References 145(2)
8 Tunneling Insertion Reaction of Carbenes 147(26)
(H. Tomioka)
8.1 Introduction 147(1)
8.1.1 Dicoordinate Carbon 147(1)
Intermediate-Carbenes
8.1.2 Carbenes Have Two-Electronic 148(1)
States Singlet and Triplet
Multiplicities
8.1.3 Singlet and Triplet States Show 149(2)
Different Reaction Patterns
8.1.4 How to Generate a Carbene 151(1)
8.2 Reactions of Arylcarbenes with 152(3)
Alkenes at 77 K
8.3 Reactions of Arylcarbenes with 155(2)
Alcohols at 77 K
8.4 Tunneling C-H Insertion from 157(3)
Triplet Carbenes at Low Temperature
8.5 Why Can Only Triplets Find a 160(1)
Tunneling Pathway?
8.6 Tunneling Reactions of Carbene 161(3)
Having Intramolecular Reaction Channels
8.7 Tunneling in Intramolecular 164(2)
Reactions
8.8 Tunneling Reaction at Elevated 166(4)
Temperatures
8.9 Conclusion and Future Development 170(1)
References 171(2)
9 Production of Interstellar Molecules and 173(28)
Amorphous Semiconductors by Atom Tunneling
Reaction (K. Hiraoka)
9.1 Introduction 173(2)
9.2 Method 175(2)
9.3 Laboratory Simulation of H-atom 177(1)
Tunneling Reactions in Interstellar Ices
9.3.1 Gas-Grain Processes for the 178(4)
Formation of NH3, CH4, and H2O
9.3.2 Formation of Formaldehyde by the 182(2)
Tunneling Reaction of H with Solid CO
at 10 K
9.3.3 Tunneling Reactions of H Atoms 184(5)
with Solid C2H2, C2H4, and C2H6
9.3.4 Tunneling Reactions of D Atoms 189(1)
with C2H2, C7H4 and C2H6: isotope Effect
9.3.5 Negative Temperature Dependence 190(3)
of H-Atom Tunneling Reactions
9.4 Formation of Amorphous 193(4)
Semiconductor by H-Atom Tunneling
Reactions
9.5 Conclusion and Future Development 197(1)
References 198(3)
10 Atom Tunneling and Molecular Structure (H. 201(32)
Sekiya)
10.1 Introduction 201(1)
10.2 Experimental Methods 201(5)
10.3 Proton Tunneling in Molecules and 206(1)
Complexes
10.3.1 Proton Tunneling in Molecules 206(1)
10.3.2 Proton Tunneling in Complexes 219(8)
10.4 Conclusion and Future Development 227(1)
References 228(5)
11 Atom Tunneling and Crystalline Structure 233(30)
(T. Matsuo)
11.1 Introduction 233(1)
11.2 General Considerations on X-Ray and 234(3)
Neutron Diffraction, Crystal Structure
and Phase Transitions
11.3 Proton Tunneling in Hydrogen-Bonded 237(8)
Crystals
11.4 Tunneling Energy Levels of Ammonium 245(6)
Ions In Ammonium Hexachlorometallates:
Global and Local Rotation and Tunneling
11.5 Delocalization of H (D) Atoms. 251(6)
Structure of (NH4)2PtCI6, (NH4)2SnC16 and
(ND4)2SnCI6 by Neutron Diffraction
11.6 Other Compounds Possessing Strong 257(1)
isotope-Dependent Properties
11.7 Conclusion and Future Development 258(1)
References 258(5)
Part 3 Atom Tunneling In Biology
12 Atom Tunneling Reaction of Vitamin C in 263(22)
Suppression of Mutation (T. Miyazaki and J.
Kumagai)
12.1 Introduction 263(1)
12.1.1 Tunneling Reaction at Room 263(1)
Temperature
12.1.2 How to Study Tunneling Reactions 265(2)
in Biological Systems
12.2 Long-Lived Radicals in 267(1)
γ-Irradiated Cells
12.2.1 Discovery of Long-Lived Radicals 267(1)
and Reactions with Vitamin C
12.2.2 Why Do Reactive Radicals Survive 269(1)
for a Long Time?
12.2.3 Assignment of Long-Lived Radicals 272(3)
12.3 Reaction of Long-Lived Radicals with 275(2)
Vitamin C
12.4 Biological Effects of Tunneling 277(3)
Reaction of Long-Lived Radicals with
Vitamin C
12.5 Tunneling Reaction of Long-Lived 280(2)
Radicals with Vitamin C
12.6 Conclusion and Future Development 282(1)
References 283(2)
13 Atom Tunneling Reaction of Vitamin E in 285(20)
Antioxidant, Prooxidant and Regeneration
Reactions (S. Nagaoka)
13.1 Introduction 285(4)
13.2 Tunneling Antioxidant Reaction of 289(6)
Vitamin E
13.3 Prooxidant Reaction of Vitamin E 295(3)
13.4 Tunneling Regeneration Reaction of 298(3)
Vitamin E
13.5 Conclusion and Future Development 301(1)
References 302(3)
Index 305