Molin Yu.N., Salikhov K.M., Zamaraev K.I. Spin Exchange (Berlin; New York, 1980) - ОГЛАВЛЕНИЕ / CONTENTS
 Навигация
 
Ю.Н.Молин
Molin Yu.N. Spin Exchange. Principles and Applications in Chemistry and Biology / Molin Yu.N., Salikhov K.M., Zamaraev K.I. - Berlin; New York: Springer-Verlag, 1980. - 242  p. - (Springer Series in Chemical Physics; Vol.8)
 
   Оглавление книгиИсточник

  1. Introduction ................................................ 1

  2. Theory of Spin Exchange .................................... 11

    2.1 Exchange Interaction Between Two Paramagnetic Particles   11
        Dependence of Interaction Energy on Spin ................ 11
        Spin-Hamiltonian of Exchange Interaction ................ 13
        The Nature of Exchange Interaction. 
        The Two-Electron System ................................. 13 
        Interaction Between Many-Electron Systems.
        Delocalization and Spin Polarization .................... 16
        Anisotropy of Exchange Interaction ...................... 19
        Semiempirical Estimates of Exchange Integral ............ 20
    2.2 Qualitative Description of Spin Exchange Process ........ 25
        Spin Exchange ........................................... 25
        Spin Exchange in a Two-Electron System .................. 26
        Spin Density Matrix ..................................... 28
        Spin Motion Due to Exchange Interaction ................. 30
    2.3 Formal Kinetics of Spin Exchange in Magnetically
        Dilute Solutions ........................................ 34
        Binary Collision Approximation .......................... 34
        Rate of Bimolecular Spin Exchange Process ............... 35
        Kinetics of Spin Exchange for Particles with Spins S=1/2  36
        Kinetic Equations for Free Radicals Showing Hyperfine
        Structure (HFS) in Their ESR Spectra .................... 40
    2.4 Spectroscopic Manifestations of Spin Exchange ........... 41
        Spectral Diffusion Due to Spin Exchange ................. 41
        Shape of ESR Spectra .................................... 42
        Slow Exchange ........................................... 45
        Fast Exchange ........................................... 48
        Other Methods of Measuring the Rate of Spin Exchange .... 49
        Effect of Saturation .................................... 50
        Electron-Electron Double Resonance (ELDOR) .............. 53
        Electron Spin Echo ...................................... 55
    2.5 Theory of Sudden Collisions ............................. 56
        2.5.1 Model of Sudden Collisions ........................ 56
              Basic Assumptions ................................. 56
              Equations for the Estimation of τc ................ 58
        2.5.2 Kinetic Equations ................................. 61
              Steady-State Equation for the Operator of 
              Collision Efficiency .............................. 64
        2.5.3 Spin Exchange Between Radicals .................... 65
              Model System ...................................... 65
              Spin Exchange Between Radicals in the Presence
              of Hyperfine Interaction .......................... 70
        2.5.4 Spin Exchange Between Radicals with Anisotropic
              Interaction ....................................... 70
              Rotation of Partners at the Moment of 
              Their Contact ..................................... 71
              Orientational Relaxation of Particles in 
              Intervals Between Reencounters .................... 78
        2.5.5 Spin Exchange of Radicals with Other
              Paramagnetic Particles ............................ 82
              Spin Exchange Between Radicals and Spins SB with
              Long Times of Paramagnetic Relaxation ............. 83
              Shape of ESR Spectra .............................. 85
              The Influence of the Relaxation of Spin SB on
              the Rate of Exchange .............................. 87
              Anisotropy of Spin Exchange ....................... 90
        2.5.6 Spin Exchange in Biradicals ....................... 91
              The Model ......................................... 92
              Kinetic Equations ................................. 93
              The ESR Spectrum of Nitroxide Biradicals .......... 94
    2.6 The Model of Diffusive Passage .......................... 96
        The Model ............................................... 97
        An Equation for the Operator of Collision Efficiency .... 98
        The Kinetic Equations ................................... 99
        The Spin Exchange Between Two Kinds of Particles with
        Spins SA = SB = 1/2 ...................................... 99
        Comparison of Results Obtained from Models of Sudden
        Collisions and Those of Diffusive Passage .............. 103

  3. Experimental Measurement of Spin Exchange Rate ............ 107

       3.1 Experimental Measurement of Spin Exchange Rate
           Constants from ESR Spectra .......................... 107
           3.1.1 Exchange Between Identical Particles
                 with S = 1/2 .................................. 107
                 Doublet Spectrum with a Zero Initial Width .... 107
                 Complex Spectra ............................... 110
                 Determination of Rate Constants from Exchange
                 Broadening of Complex Spectra ................. 111
                 Determination of Rate Constants from Exchange
                 Shift of the Lines of Complex Spectra ......... 116
                 Determination of Rate Constants from Exchange
                 Narrowing of Complex Spectra .................. 117
                 Peculiarities of Exchange Narrowing in 
                 Concentrated Solutions ........................ 118
                 Comparison of Spin Exchange Rate Constants 
                 Measured by Different Techniques .............. 119
           3.1.2 Exchange Between Different Particles .......... 120
       3.2 Other Methods of Measuring the Spin Exchange Rate
           Constants ........................................... 127
           3.2.1 Continuous Wave Saturation Method ............. 127
           3.2.2 Electron-Electron Double Resonance ............ 130
           3.2.3 Electron Spin Echo ............................ 132
       3.3 Separation of Exchange and Dipole-Dipole
           Contributions to Concentration Broadening of ESR
           Lines ............................................... 133
           Theoretical Estimation of Dipole Broadening ......... 134
           Experimental Estimation of Dipole-Dipole
           Contribution at Low Viscosity ....................... 137
           Separation of the Cases of Exchange and Dipole -
           Dipole Broadening According to Viscosity and
           Temperature Dependences ............................. 139
       3.4 Separation of the Cases of Weak and Strong Exchange   142

  4. Spin Exchange in Chemistry and Biology .................... 147

       4.1 Study of Diffusion Collisions in Solutions .......... 148
           Hydrodynamic Model of Diffusion Collisions .......... 148
           Potentialities of Spin Exchange ..................... 149
           4.1.1 Collisions in Single-Component Solvents ....... 152
                 Spin Exchange Between Radicals ................ 152
                 Spin Exchange Between Free Radicals and
                 Paramagnetic Complexes ........................ 158
           4.1.2 Collisions in Complex Systems ................. 165
                 Binary Solvents ............................... 166
                 Liquids Near Critical Points .................. 168
                 Polymeric and Heterogeneous Systems ........... 171
                 Collisions of Macroradicals ................... 173
           4.1.3 Study of Intramolecular Collisions of 
                 Paramagnetic Fragments ........................ 175
       4.2 Estimation of the Energy of Exchange Interaction 
           During Collisions ................................... 178
           4.2.1 Free Radicals ................................. 180
           4.2.2 Spin Exchange with Metal Complexes ............ 182
           4.2.3 Discussion of Results ......................... 187
       4.3 Collisions of Charged Particles ..................... 192
           4.3.1 Experimental Results .......................... 193
                 Spin Exchange in Solutions of Anion Radical
                 (SO3)2NO2- ..................................... 193
                 Spin Exchange Involving Charged Nitroxide 
                 Radicals ...................................... 198
                 Spin Exchange Between Anion Radicals in
                 Organic Solvents .............................. 203
           4.3.2 Comparison of Experiments on Spin Exchange
                 with the Diffusion Theory of Collisions
                 of Charged Particles in Liquid ................ 204
           4.3.3 Study of Collisions Between Aquo Complexes
                 of Transition Metals .......................... 207
                 Role of Counterions in Collisions of Aquo
                 Complexes of Vanadyl .......................... 207
                 An Example of the Process with Weak Influence
                 of Electrostatic Repulsion .................... 211
       4.4 Biological Applications of Spin Exchange ............ 213
           Paramagnetics Used as Spin Probes ................... 214
           4.4.1 Measurement of Binary Collision Rate of 
                 Molecules in Biological Systems ............... 214
           4.4.2 Study of Location of Paramagnetic Centers
                 in Bio-polymers ............................... 217
                 Quantitative Interpretation of the Values
                 of Ke for Spin Exchange Processes
                 Involving Paramagnetic Centers of Biopolymers   220
           4.4.3 "Development" of Individual ESR Spectra
                 of Spin Labels via Spin Exchange .............. 222
           4.4.4 Spin Exchange Titration ....................... 225
                 Kinetics of Reactions Involving Oxygen 
                 Molecules ..................................... 225
                 Coordination of Paramagnetic Ions by 
                 Macromolecules ................................ 226
           4.4.5 Other Applications ............................ 227
       4.5 Conclusion .......................................... 228

   List of Frequently Used Notations and Abbreviations ......... 231
   References .................................................. 233
   Subject Index ............................................... 241


 вверхMolin Yu.N. Spin Exchange. Principles and Applications in Chemistry and Biology / Molin Yu.N., Salikhov K.M., Zamaraev K.I.. - Berlin; New York: Springer-Verlag, 1980. - 242 p. - (Springer Series in Chemical Physics; Vol.8).
 
Spin Exchange (Berlin - New York, 1980)
 

Научные школы ННЦ Ю.Н.Молин | Указатель трудовПодготовили Клара Елкина и Сергей Канн  
 


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