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(Download PDF) Epr Spectroscopy Fundamentals and Methods 1St Edition Daniella Goldfarb Online Ebook All Chapter PDF
(Download PDF) Epr Spectroscopy Fundamentals and Methods 1St Edition Daniella Goldfarb Online Ebook All Chapter PDF
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Table of Contents
Cover
Title Page
Copyright
eMagRes Books
International Advisory Board
Contributors
Series Preface
Preface
Abbreviations and Acronyms
Part A: Fundamental Theory
Chapter 1: Continuous-Wave EPR
1.1 Introduction
1.2 Basic Design and Operation of a CW-EPR Spectrometer
1.3 Solution Spectra
1.4 The Effect of Motion on CW-EPR Spectra
1.5 Spectra of Solids
1.6 Concluding Remarks
Acknowledgment
Further Reading
References
Chapter 2: EPR Interactions – g-Anisotropy
2.1 Introduction
2.2 The Zeeman Interaction for Spin ½
2.3 g-Anisotropy in the Solid State
2.4 g-Anisotropy in the Liquid State
2.5 Fictitious Spin ½
2.6 The Origin of the g-Anisotropy
References
Chapter 3: EPR Interactions – Zero-field Splittings
3.1 Introduction
3.2 Effects of ZFS on the EPR Spectrum
3.3 Origins of ZFS
3.4 Examples of ZFS in Actual Systems
3.5 Conclusion
Acknowledgments
3.6 Recommended Reading
References
Chapter 4: EPR Interactions – Coupled Spins
4.1 Introduction
4.2 The Isotropic Exchange Interaction
4.3 Two Coupled Spins si: The Hamiltonian Matrix and
EPR
4.4 Coupling Two General Spins
4.5 Coupling More than Two Spins
4.6 Relationship between Spin Hamiltonian Parameters of
the Total Spin States and those of the Uncoupled
Paramagnets
4.7 Breakdown of the Strong Exchange Limit
4.8 Other Terms in the Exchange Hamiltonian
4.9 Noncoincidence Effects between the Interaction
Matrices: g, A, J, D, Jdip, D12, etc
4.10 Exchange between Orbitally Degenerate Species
4.11 Concluding Comments
Acknowledgment
Further Reading
References
Chapter 5: EPR Interactions – Hyperfine Couplings
5.1 Introduction
5.2 Dipolar Interaction and Hyperfine Hamiltonian
5.3 EPR Transitions in the General High Magnetic Field
Case
5.4 Examples of EPR Spectra in Liquid and Frozen
Solution
5.5 Example of EPR Spectra at Multiple Frequencies
5.6 Mechanisms of Hyperfine Coupling
5.7 EPR Spectra in the Low-field Case
5.8 Transition Probabilities
Acknowledgment
Further Reading
References
Chapter 6: EPR Interactions – Nuclear Quadrupole Couplings
6.1 The Nuclear Quadrupole Interaction
6.2 Energy Levels and Spectra
6.3 Analysis of EFG Tensors
6.4 Experimental Examples – EPR Spectra
6.5 Experimental Examples – ENDOR/ESEEM Spectra
6.6 Conclusions
Acknowledgments
Further Reading
References
Chapter 7: Quantum Chemistry and EPR Parameters
7.1 Introduction
7.2 Theory
7.3 Electronic Structure Methods
7.4 Illustration: Hyperfine Couplings
7.5 Concluding Remarks
Acknowledgments
References
Chapter 8: Spin Dynamics
8.1 Introduction
8.2 The Single-Electron Spin System
8.3 Two Coupled Electrons
8.4 An Electron Coupled to a Nucleus with I = 1/2
Acknowledgments
Further Reading
References
Chapter 9: Relaxation Mechanisms
9.1 Introduction
9.2 Relaxation Processes
9.3 Relaxation of Triarylmethyl (Trityl) Radicals
9.4 Relaxation of Semiquinones
9.5 Relaxation of Nitroxides
9.6 Relaxation of Cu(II) Complexes
9.7 Relaxation of Iron–Sulfur Clusters
9.8 Relaxation in Irradiated Organic Solids
9.9 Metals with S > ½
9.10 Summary
Acknowledgments
References
Part B: Basic Techniques and Instrumentation
Chapter 10: Transient EPR
10.1 Introduction
10.2 Experimental Considerations
10.3 Applications of Transient EPR
10.4 Conclusions
Acknowledgments
References
Chapter 11: Pulse EPR
11.1 Introduction
11.2 Pulses and Spins
11.3 Basic Pulse Sequences
11.4 Bandwidths
11.5 Non-Coherent Effects
11.6 Spectrometer
11.7 Practical Aspects
11.8 Further Reading
Acknowledgments
References
Chapter 12: EPR Instrumentation
12.1 Introduction
12.2 Magnet Systems
12.3 Microwave Bridges
12.4 EPR Resonators
12.5 Sample Cryostats
12.6 Spectrometer Control and Signal Detection
12.7 Instrumentation for Special Applications
Further Reading
References
Chapter 13: EPR Imaging
13.1 Introduction
13.2 Brief History
13.3 Basics of Image Acquisition
13.4 Spin Probes
13.5 Imaging Instrumentation and Methodology
13.6 Applications
13.7 Conclusion
Acknowledgments
References
Chapter 14: EPR Spectroscopy of Nitroxide Spin Probes
14.1 Introduction
14.2 Types of Nitroxide Probes
14.3 The Hamiltonian Describing the Nitroxide Spectrum
14.4 Dynamics of the Nitroxide Probe Encoded in the
Spectral Linewidth
14.5 Polarity and Proticity of the Nitroxide
Microenvironment Extracted from g and A Tensor
Parameters
14.6 Techniques to Monitor Water Accessibility Toward
the Nitroxides
14.7 Concluding Remarks
Acknowledgments
References
Part C: High-Resolution Pulse Techniques
Chapter 15: FT-EPR
15.1 Introduction
15.2 Single Pulse, S = 1/2
15.3 Multipulse FT-EPR
15.4 S > 1, Triplets and Interacting Radicals
15.5 Digital FT
15.6 FT-EPR Examples
Acknowledgments
Further Reading
References
Chapter 16: Hyperfine Spectroscopy – ENDOR
16.1 Introduction
16.2 Static Spin Hamiltonian and the Nuclear Frequencies
16.3 CW ENDOR
16.4 Pulse ENDOR Techniques
References
Chapter 17: Hyperfine Spectroscopy – ELDOR-detected NMR
17.1 Introduction
17.2 The EDNMR Experiment
17.3 EDNMR for I > 1/2
17.4 Experimental Considerations
17.5 EDNMR versus Pulse ENDOR
17.6 EDNMR versus ESEEM
17.7 Simulations
17.8 Two-dimensional Experiments
Acknowledgments
References
Chapter 18: Hyperfine Spectroscopy – ESEEM
18.1 Introduction
18.2 Basic 1D ESEEM Experiments
18.3 Four-pulse ESEEM
18.4 Improving the Performance of ESEEM
Acknowledgments
References
Chapter 19: Dipolar Spectroscopy – Double-resonance
Methods
19.1 Introduction
19.2 Dilute Cluster Description of the Sample
19.3 Pulse Sequences
19.4 Expressions for Dipolar Evolution
19.5 Orientation Selection
19.6 Complications and Remedies
19.7 Spins S > ½
19.8 Data Analysis
19.9 Conclusions
Acknowledgments
Further Reading
References
Chapter 20: Dipolar Spectroscopy – Single-resonance
Methods
20.1 Introduction
20.2 Basic Theoretical Aspects of PDS Methods
20.3 Double-quantum Coherence EPR, Six-pulse Sequence
20.4 Four- and Five-pulse ‘Single-quantum Coherence’
PDS Sequences
20.5 Other Single-frequency PDS Methods
20.6 2D-FT Orientation-correlation PDS
20.7 Relaxation and Instantaneous Diffusion
20.8 Conclusions
Acknowledgments
References
Chapter 21: Shaped Pulses in EPR
21.1 Introduction
21.2 Specific Types of Pulses
21.3 Instrumentation
21.4 Applications of Shaped Pulses in EPR
21.5 Future Outlook
Acknowledgments
References
Part D: Special Techniques
Chapter 22: Pulse Techniques for Quantum Information
Processing
22.1 Spin Qubits
22.2 Decoherence
22.3 Measuring Gate Fidelities
22.4 High-fidelity Operations
22.5 Sensing
22.6 Multiple Qubits
22.7 Conclusions
Acknowledgments
References
Chapter 23: Rapid-scan EPR
23.1 Introduction
23.2 Advantages of Rapid Scan Relative to Conventional
CW Spectroscopy
23.3 Why Does Rapid Scan Give Improved S/N?
23.4 Hardware and Software Used in Rapid Scan
23.5 Parameter Selection
23.6 Extending Rapid Scan to Wider Spectra
23.7 Rapid Frequency Scans
23.8 Future
Acknowledgments
References
Chapter 24: EPR Microscopy
24.1 Preface
24.2 Introduction
24.3 Pulse EPR Microscopy: Theory
24.4 Pulse EPR Microscopy: Practice
24.5 Experimental Examples for EPRM Applications
24.6 Conclusions and Future Prospects
References
Chapter 25: Optically Detected Magnetic Resonance (ODMR)
25.1 Introduction
25.2 Instrumentation
25.3 ODMR of Triplet States in Molecules and Crystals
25.4 ODMR of Half-integer Spin Systems
25.5 ODMR of Interacting Spin Pairs
Acknowledgments
References
Chapter 26: Electrically Detected Magnetic Resonance
(EDMR) Spectroscopy
26.1 Introduction
26.2 A Brief History of EDMR Spectroscopy
26.3 Electronic Mechanisms that Cause EDMR Signals
26.4 Continuous-wave EDMR
26.5 Pulse EDMR
26.6 Radio Frequency EDMR
26.7 Conclusions and Outlook
Acknowledgments
References
Chapter 27: Very-high-frequency EPR
27.1 Introduction
27.2 Benefits of VHF-EPR
27.3 VHF-EPR Spectrometers
27.4 Further Reading and Outlook
Acknowledgments
References
Index
End User License Agreement
List of Illustrations
Chapter 1: Continuous-Wave EPR
Figure 1.1 Schematic diagram of a simple CW-EPR
spectrometer.
Figure 1.2 Tuning mode patterns for different coupling
regimes: (a) undercoupled; (b) critically coupled; and (c)
overcoupled
Figure 1.3 Magnetic and electric field intensity distribution in
a TE102 rectangular resonator
Figure 1.4 Field modulation of an EPR absorption line. (a) A
Gaussian absorption line and the modulated signal at several
positions in the line. (b) The resulting derivative-like line
shape produced by the lock-in amplifier
Figure 1.5 The influence of the field-modulation amplitude on
the intensity and shape of the EPR spectrum. The spectra are
of a sample of DPPH (2,2-diphenyl-1-picrylhydrazyl)
measured with the field-modulation amplitudes given above
each trace
Figure 1.6 The EPR signal intensity and line shape as a
function of the microwave power. (a) Saturation curve
calculated using equation (1.6) with P1/2 = 24.8 mW and b =
1.44. (b) Spectra calculated using the steady-state solution of
the Bloch equations with T1 = T2 = 50 ns and ωres/ħgeμB =
352 mT
Figure 1.7 Calculated spectra of a nitroxide radical showing
the effect of molecular motion as a function of the rotational
correlation time τc. The spectra have been calculated using
EasySpin13 and the principal g values (gxx = 2.0089, gyy =
2.0061, gzz = 2.0027) and 14N hyperfine couplings (Axx = 14.6
MHz, Ayy = 14.6 MHz, Azz = 86.9 MHz) are taken from the
literature18
Figure 1.8 Characteristic powder patterns for S = 1/2 and the
different possible symmetries of the g-tensor
Figure 1.9 Calculated spectra of copper(II) porphyrin showing
the contribution of hyperfine coupling. (a) The spectrum in
the absence of hyperfine coupling. (b) The spectrum with
hyperfine coupling to the I = 3/2 copper nucleus included. (c)
The spectrum with hyperfine coupling to Cu and four
equivalent coordinating N atoms from the porphyrin ring.
Principal g values of Cu(II): 2.03, 2.03, 2.19; principal values
of the Cu hyperfine coupling (MHz): 75, 75, 608; N hyperfine
coupling (isotropic) 40 MHz
Figure 1.10 Rhombogram and example spectrum for S = 3/2.
The spectrum is calculated for E/D = 0.32 and D = −1.1 × 105
MHz. Microwave frequency = 9.75 GHz. The features at geff =
5.4 arise from the mS = ±1/2 transition with the field along
the x-direction and the mS = ±3/2 transition with the field
along z. The peak at geff = 1.93 is from mS = ±1/2, y and mS =
±3/2, y and x. The feature at geff = 1.43 is from mS = ±1/2, z
Chapter 2: EPR Interactions – g-Anisotropy
Figure 2.1 (a) Experimental continuous-wave EPR spectrum
of azurin recorded at 20 K and at 275 GHz; (b) to (d).
Simulated fields of resonance at 275 GHz as a function of the
orientation of the magnetic field in the principal planes of the
g-tensor, the yz-, the xy-, and the zx-plane with parameters:
gx = 2.0393, gy = 2.0568, gz = 2.273, intrinsic linewidth = 5
mT
Figure 2.2 Continuous-wave EPR spectra of the nitroxide
radical TEMPOL in a frozen water solution at different
microwave frequency/magnetic field settings. Spectra are
plotted relative to the fixed gz value.
Figure 2.3 (a) Wulffnet projection of the orientation of the
principal axes of the g-tensors of the azurin molecules in the
P212121 unit cell with respect to the crystallographic a, b, and
c axes. The open symbols indicate the directions of the x axes,
the shaded symbols those of the z axes. The different symbols
refer to the four molecules in the asymmetric unit, and a total
of 16 molecules in the unit cell. All points lie at the front side
of the globe. The direction of the crystallographic axes has
been derived from the direction of the g-tensor axes as
obtained by EPR. (b) The direction of the g-tensor axes in the
copper site. The copper is bound to two histidine nitrogens, a
cysteine sulfur, and a methionine sulfur
Figure 2.4 Continuous-wave EPR spectra at 275 GHz of
TEMPONE in H2O/glycerol (50/50% v/v) as a function of
temperature.
Figure 2.5 Simulations of the EPR spectrum of an S = ½
radical in the slow-motion regime at 275 and 36 GHz using
Easyspin.7 Conditions gx = 2.0083, gy = 2.0058, gz = 2.0030,
intrinsic linewidth = 0.1 mT; values of the rotation–
correlation time, τc, are given in the figure
Figure 2.6 Multifrequency EPR spectra of 131R2-labeled T4
Lysozyme recorded in 25 w/v% Ficoll solution at 2, 12, 22, and
32 °C; experimental data (solid lines), simulations (dashed
lines).
Figure 2.7 Continuous-wave EPR spectrum of a powder
sample of at X-band and 8 K
Figure 2.8 Schematic representation of the atomic orbitals
involved in the singly occupied molecular orbitals for the NO
bond in the ground state and the excited state: the 2pz orbitals
on nitrogen and oxygen and the lone-pair orbitals n and n′ on
oxygen
Figure 2.9 Schematic representation of the atomic orbitals
involved in the singly occupied molecular orbital for the CuS
bond in the ground state: the 3dxy orbital on copper and the
3py orbital on sulfur. For azurin, the copper is less than 0.1 Å
above the NNS (xy)-plane, and the drawing is a projection on
this plane
Chapter 3: EPR Interactions – Zero-field Splittings
Figure 3.1 X-band EPR spectrum of a powder of [Ni(NH3)6]I2
(black trace) recorded at 77 K, 9.235 GHz, with simulation
(red trace) generated using S′ = 1/2, g = 2.126, W = 800 MHz
(Lorentzian, hwhm)
Figure 3.2 Relative energy levels in units of D of spin triplets
through sextets as a result of rhombic ZFS (|E/D| = 0.1). The
ordering is for positive D; for negative D, the order would be
reversed. The energy values for triplets through quintets are
exact; those for the sextet use second-order perturbation
theory but are accurate to within a few percent of an exact
calculation
Figure 3.3 Diagrams of energy levels (eigenvalues) as a
function of external magnetic field for a spin triplet with the
following spin Hamiltonian parameters: S = 1, giso = 2.00,
D/hc = +0.15 cm−1, upper plot: E = 0; lower plot: E/hc =
+0.025 cm−1. Black lines indicate energies with the magnetic
field along the ZFS z-axis (parallel) in both plots; in the upper
plot, blue traces indicate energies with the magnetic field
along the ZFS x-axis (= y-axis; perpendicular); in the lower
plot, green traces are for the field along the ZFS x-axis and red
traces for the field along the ZFS y-axis. Arrows indicate
allowed EPR transitions with a microwave quantum of 9.3
GHz (0.31 cm−1), with their colors corresponding to the
transition orientation
Figure 3.4 X-band (9.3 GHz) EPR transition energies
calculated using EasySpin for a spin triplet with g = 2.00,
D/hc = 0.15 cm−1 as a function of the angle θ between the
external magnetic field and the ZFS tensor z-direction. The
correspondence between transitions labels z1 (red trace) and
z2 (blue trace) and ΔmS = ±1 transitions (where this is a good
quantum number, i.e., at θ = 0°) is indicated
Figure 3.5 Simulated EPR spectra for a spin triplet with giso =
2.00, axial ZFS, D/hc = +0.15 cm−1; with rhombic splitting
(E/hc = +0.015 cm−1; green traces) and without rhombic
splitting (red traces). Single-crystal Gaussian linewidths
(hwhm) of 100 MHz were used. A typical X-band microwave
frequency of 9.3 GHz (≈0.31 cm−1) was used. Both an
absorption presentation (lower traces) and a first derivative
(upper traces) are shown. The turning points are labeled using
standard nomenclature for triplets.29 The relation between
splittings of some of the turning points and ZFS parameters is
also indicated. These splittings are shown in magnetic field
quantities, not in energy, and thus need to be converted to
energy quantities using gμB as described in the text
Figure 3.6 Simulated EPR spectra (absorption presentation)
for spin triplets with axial ZFS. The D/hc values (in cm−1) are
indicated in the figure; isotropic g = 2.00; single-crystal
Gaussian linewidths (hwhm) of 100 MHz; microwave
frequency 9.3 GHz (≈0.31 cm−1). The spectra are calculated
using a powder pattern with the single-crystal resonant fields
along the canonical ZFS tensor axes indicated by red bars. The
turning points are labeled using a standard nomenclature for
triplets
Figure 3.7 Diagrams of energy levels (eigenvalues) as a
function of external magnetic field for a spin quartet with the
following spin Hamiltonian parameters: S = 3/2, giso = 2.00,
D/hc = +0.15 cm−1, upper plot: E = 0; lower plot: E/hc =
+0.025 cm−1. Black lines indicate energies with the magnetic
field along the ZFS z-axis (parallel) in both plots; in the upper
plot, blue traces indicate energies with the magnetic field
along the ZFS x-axis (perpendicular); in the lower plot, green
traces are for the field along the ZFS x-axis and red traces for
the field along the ZFS y-axis. Arrows indicate allowed EPR
transitions with a microwave quantum of 9.3 GHz, with their
colors corresponding to the transition orientation
Figure 3.8 Simulated EPR spectra for a spin quartet with giso
= 2.00, axial ZFS, D/hc = +0.10 cm−1; with rhombic splitting
(E/hc = +0.010 cm−1; green traces) and without rhombic
splitting (red traces). Single-crystal Gaussian linewidths
(hwhm) of 100 MHz were used. A typical X-band microwave
frequency of 9.3 GHz (≈0.31 cm−1) was used. Both an
absorption presentation (lower traces) and a first derivative
(upper traces) are shown. The turning points are labeled using
standard nomenclature for quartets; green labels are unique
to the rhombic case; red labels are unique to the axial case;
and black labels are common to both. The asterisk indicates
an off-axis turning point (Figure 3.9). The approximate
relation between splittings of the turning points and ZFS
parameters is also indicated. These splittings are shown in
magnetic field quantities, not in energy, and thus need to be
converted to energy quantities using gμB as described in
Section 3.2.1.3
Figure 3.9 X-band (9.3 GHz) EPR transition energies
calculated using EasySpin for a spin quartet with g = 2.00,
D/hc = 0.10 cm−1 as a function of the angle θ between the
external magnetic field and the ZFS tensor z-direction. The
horizontal dashed line indicates the angle (θ ≈ 39°) where
there is significant spectral intensity that does not correspond
to either a parallel (θ = 0°) or a perpendicular (θ = 90°)
turning point, i.e., an off-axis resonance, occurring at dB/dθ =
0, as is also the case at the canonical values. The
correspondence between transitions labels z1 (green trace), z2
(red trace), and z3 (blue trace) and ΔmS = ±1 transitions
(where this is a good quantum number, i.e., at θ = 0°) is
indicated. The unlabeled traces (cyan, violet, and orange) are
less easily classified and give rise to the lower intensity
transitions as seen at low field in Figure 3.8
Figure 3.10 Simulated EPR spectra (absorption presentation)
for spin quartets with giso = 2.00, axial ZFS. The D/hc values
(in cm−1) are indicated; single-crystal Gaussian linewidths
(hwhm) of 100 MHz; microwave frequency 9.3 GHz (≈0.31
cm−1). The spectra are calculated using a powder pattern with
the single-crystal resonant fields along the canonical ZFS
tensor axes indicated by red bars. The turning points are
labeled using standard nomenclature; an off-axis turning
point (see text) is indicated by an asterisk
Figure 3.11 Simulated EPR spectra for a spin quartet with
axial ZFS, D/hc = +3.0 cm−1 (E = 0; g = 2.00) using both 35
GHz (green traces; 2 T field sweep) and 330 GHz (red traces;
20 T field sweep). Single-crystal Gaussian linewidths (fwhm)
of 300 MHz were used for the 35-GHz spectrum and 3000
MHz for the 330-GHz spectrum. Both an absorption
presentation (lower traces) and a first derivative (upper
traces) are shown. All intensities are arbitrarily scaled. The
turning points are labeled using standard nomenclature for
quartets. The 35- GHz spectrum is not labeled; its
(2.030 2.033 2.120), (Ax, Ay, Az) = (−43, −76, 423) MHz, (Px,
Py, Pz) = (−7.17, −7.17, +14.34) MHz, and all tensors were
taken as collinear. The blue spectrum was calculated with (Px,
Py, Pz) = (0,0,0)
Figure 6.9 (a) Schematic structure of Cu2RGT. The
exchangeable protons are indicated in red. (b) The W-band
echo-detected EPR spectrum of Cu2RGT measured at 6.5 K,
(c) 2H-Mims W-band ENDOR spectrum of Cu2RGT/D2O
recorded at g|| (B0 = 3.386 T), labeled in (b), and the
corresponding simulations (red lines) obtained with the
parameters (Ax, Ay, Az) = (−0.8, −0.66, −0.2) MHz, e2qQ/h =
220 kHz, η = 0.14 and the appropriate orientations of the
hyperfine and quadrupole tensors. For convenience, the
intensity was multiplied by −1. * marks an impurity signal.
Figure 6.10 (a) The Gd-DOTA complex. (b) W-band echo-
detected EPR spectrum of Gd-DOTA in the region of the
central transition recorded at 10 K. (c) W-band 14N Mims
ENDOR spectrum of Gd-DOTA, recorded at 10 K and a
magnetic field of 3407 mT, with assignments of the hyperfine,
A, and the quadrupolar, 3P, splittings. The spectral features
marked with * correspond to contributions attributed to the
mS = ±3/2 electron spin manifolds, while all other features
are due to the mS = ±1/2 electron spin manifolds (central
transition). The blue curve represents the simulation of the
ENDOR frequencies due to the central transition with the
parameters presented in the text, the green curve represents
the simulation of the contribution from the mS = ±3/2
electron spin manifolds (see text), and the red trace is their
sum. For the simulations, the anisotropic hyperfine coupling,
T⊥ = 0.30 MHz, was derived from an average Gd-N distance
of 2.66 Å obtained from the crystal structure of Gd-DOTA,27
the isotropic part was aiso = −0.37 MHz, e2Qq/h = 4.31 MHz,
and η = 0. At this field νI = 10.6 MHz.
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résoudre les difficultés de sa tâche. Alors qu’en fait le pion prépare
lui-même un examen et n’exige que le silence et la paix.
Et dans quel féroce petit monde jettent-ils ainsi leurs enfants !
Image réduite et déformée de l’humanité, où les instincts et les vices
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L’internat français prépare de mauvais hommes. Ils ne peuvent
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Oh ! Ces années, de dix à vingt ans, ces années qui devraient
être le jardin, la parure, comme le paradis de l’existence, où l’âme
devrait éclore avec ravissement, tout apprendre, tout comprendre,
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délices, ces années, des mœurs caduques les ont injustement,
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sans joie.
Le Foyer.
J’ai dit ce que je pense du lycée. L’idéal serait l’instruction par les
parents, au moins jusqu’à la quinzième année. J’entends déjà leurs
cris : « Ils n’ont pas le temps ». Ce n’est pas mon avis. Que chacun
fasse son examen de conscience. Une demi-heure par jour suffirait
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courses, en visites, en thés. Les hommes, au café, au jeu, ou chez
leurs maîtresses. On peut toujours trouver une demi-heure.
Une autre objection se dresse, assez comique. Un jour, je disais
à un de mes confrères, un écrivain très réputé, que j’avais entrepris
l’instruction de mon fils. Il m’interrompit, ingénument :
— Mais alors, vous avez dû tout rapprendre ?
Le mot est à double fond. Creusez-le. Vous y trouverez tout le
procès de l’instruction actuelle. Car enfin, si nous devons tout
rapprendre pour instruire nos enfants, c’est donc que nous avons
tout oublié. C’est donc que nos années de lycée ne nous ont servi à
rien ?
Pour les parents qui ne voudraient pas tirer leur science de leur
propre fonds, les cours par correspondance seront un guide
excellent. Certains manuels d’instruction au logis sont déjà conçus
dans un esprit lucide et pratique.
Et, je le répète, je crois beaucoup à l’enseignement par le livre,
pour celui qui s’intéresse à ce qu’il apprend. On peut approfondir,
creuser un sujet, revenir en arrière, méditer, mûrir. On n’est pas
talonné. Tandis qu’un professeur qui parle à trente élèves ne peut
pas s’occuper de chacun d’eux. Il va, il va. Il sème. Tant pis si sa
parole ne germe pas.
La Valise.
Comment apprendre.
Afin que les adolescents ne soient pas poussés tous vers les
mêmes professions, afin d’élargir leur choix, il serait bon de montrer
ce qu’il y a d’inconséquent et souvent de stupide dans la hiérarchie
des métiers, telle qu’elle s’est installée dans l’estime publique.
Car cette hiérarchie existe. On en a une preuve curieuse dans la
rédaction des lettres mortuaires. Dans l’énumération de la famille, on
fait figurer les titres des officiers, des magistrats, et on se garde bien
de mentionner les industriels, les commerçants, les agriculteurs, les
ingénieurs même.
Par quelle lente stratification de préjugés cette hiérarchie s’est-
elle établie ?
Les professions les plus honorées sont-elles les plus
périlleuses ? Non. Car les tables de mortalité nous apprennent que
le pourcentage le plus élevé dans la paix est atteint par les
couvreurs et les vidangeurs.
Celles qui ont exigé le plus de travail préalable ? Non. Car le
professeur de lycée, qui a passé par Normale supérieure et fourni un
labeur écrasant, ne vient pas en tête de liste.
Celles qui exigent le plus de désintéressement ? Non. Car les
fonctionnaires, également peu payés, ne jouissent pas d’un prestige
culminant.
Les plus fructueuses ? Non. Car on n’estime pas spécialement
les financiers.
Les plus puissantes ? Non. Car les hommes armés du plus vaste
pouvoir sont les journalistes et les policiers.
Tant de raisons complexes ont joué dans ce classement ! Il y a
des carrières qui furent brillantes dans le passé et qui gardent un
éclat persistant : la carrière diplomatique, bien que ses mœurs
soient surannées, son rôle, hélas ! souvent vain et parfois
dangereux.
Puis il y a des titres qui inspirent d’autant plus de respect qu’on
les comprend moins : Conseiller référendaire à la Cour des
Comptes.
D’autres préjugés viennent d’un passé plus lointain. Si le
commerce ne jouit pas de plus d’estime, c’est peut-être qu’il était
exercé dans les anciennes civilisations par des esclaves.
Enfin, la vieille supériorité de l’âme sur le corps a exalté
démesurément le travail de l’esprit et rejeté dans l’ombre le métier
manuel.
Qu’en conclure ? Que cette hiérarchie s’est assise sous cent
influences complexes, illogiques, et qu’il faut puiser, dans le
sentiment de cette incohérence, la force de s’affranchir de ses
décrets.