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Published on 09 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782622475-FP001
Molecular Approaches
Cross-relaxation and Cross-correlation Parameters in NMR
View Online
New Developments in NMR
Editor-in-Chief:
William S. Price, University of Western Sydney, Australia
Series Editors:
Sharon Ashbrook, University of St Andrews, UK
Bruce Balcom, University of New Brunswick, Canada
István Furó, Industrial NMR Centre at KTH, Sweden
Masatsune Kainosho, Tokyo Metropolitan University, Japan
Maili Liu, Chinese Academy of Sciences, Wuhan, China
Titles in the Series:

1: Contemporary Computer-Assisted Approaches to Molecular Structure
Elucidation
2: New Applications of NMR in Drug Discovery and Development
3: Advances in Biological Solid-State NMR
4: Hyperpolarized Xenon-129 Magnetic Resonance: Concepts, Production,
Techniques and Applications
5: Mobile NMR and MRI: Developments and Applications
6: Gas Phase NMR
7: Magnetic Resonance Technology: Hardware and System
Component Design
8: Biophysics and Biochemistry of Cartilage by NMR and MRI
9: Diffusion NMR of Confined Systems: Fluid Transport in Porous Solids
.
and Heterogeneous Materials

10: NMR in Glycoscience and Glycotechnology
11: Fast NMR Data Acquisition: Beyond the Fourier Transform
12: Cross-relaxation and Cross-correlation Parameters in NMR:
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Cross-relaxation and
Cross-correlation Parameters
in NMR
Edited by
Daniel Canet
Universite de Lorraine, France
Email: daniel.canet@univ-lorraine.fr
.
Published on 09 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782622475-FP001 View Online
New Developments in NMR No. 12
Print ISBN: 978-1-84973-913-9

PDF eISBN: 978-1-78262-247-5
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r The Royal Society of Chemistry 2018
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Preface
Some time ago, I was asked by Professor William S. Price to be the editor of a
book about cross-correlation in NMR. I found the idea fairly interesting, but
at first (and only at first), that it might appear as a sibylline and restricted
subject. I answered Bill that cross-correlation is evidently related to (and part
of) spin relaxation but that spin relaxation was per se too broad a subject. By
contrast, it could be interesting to add cross-relaxation to the initial title of
the project. In fact, what are called cross-correlation relaxation rates can
be considered as well as pertaining to cross-relaxation. The concept of cross-
relaxation was introduced as early as 1953 by A. W. Overhauser, who had to
face controversy, because his idea was revolutionary. He predicted that, by
irradiating electron spins, nuclear spins would be enhanced by the transfer
of electron polarization. This idea was rapidly extended to cross-relaxation
among nuclear spins with the tremendous applications known as the
.
nuclear Overhauser effect (nOe), which generated a new era in nuclear

magnetic resonance (NMR) accessing unprecedented information about
molecular structure. Cross-relaxation rates depend on a single relaxation
mechanism (generally the interaction between the magnetic moments
associated with the two considered spins). By contrast, cross-correlation
rates depend on two different mechanisms and, although acting in the same
way as cross-relaxation rates, may couple quantities that are not necessarily
polarizations. Cross-correlation, discovered shortly after cross-relaxation,
was considered for some time as a scientific curiosity. It then appeared that
cross-correlation rates can provide invaluable dynamical and structural
information. Relevant theoretical and experimental developments followed,
eventually leading to line-narrowing phenomena that proved decisive for the
NMR observation of larger and larger biomolecules.
This book is divided into four chapters. The first chapter, by nature
introductive, is an overview of nuclear spin relaxation with an emphasis on

Cross-relaxation and Cross-correlation Parameters in NMR: Molecular Approaches
Edited by Daniel Canet
Published by the Royal Society of Chemistry, www.rsc.org
v
View Online
vi Preface
cross-relaxation and cross-correlation. The next two chapters are devoted to

cross-relaxation and cross-correlation in small or medium-size molecules,
chapter two in homonuclear systems and chapter three in heteronuclear
systems. The final chapter (Chapter 4) deals with the important impact of
cross-relaxation and cross-correlation in biological systems. We hope to have
covered all theoretical, conceptual and experimental aspects of this still

growing topic. Many examples illustrate its considerable possibilities. In
addition, the reader will find different theoretical approaches (leading
nevertheless to the same results), corresponding to the sensitivity of each
author; this should be helpful for fully understanding the rich literature on
this subject.
Daniel Canet
.
Contents
Chapter 1 Introduction to Nuclear Spin Cross-relaxation and

Cross-correlation Phenomena in Liquids 1
Daniel Canet
1.1 A Survey of Nuclear Spin Relaxation Mechanisms

and the Concept of Spectral Densities 2
1.1.1 Interaction with Local Randomly Fluctuating
Magnetic Fields 3
1.1.2 Dipolar Interactions 6
1.1.3 Chemical Shift Anisotropy (CSA) 8
1.1.4 The Spin-rotation Relaxation Mechanism 9
1.1.5 Correlated Mechanisms 10
1.2 An Introduction to Spin 1/2 Quantum Mechanics 11
.
1.2.1 Operators for a Single Spin 1/2 11

1.2.2 Product-operators for a System Involving
Several Spins 1/2 15
1.2.3 Product-operators for a Two Spin 1/2 System
and Relevant Spin States 16
1.2.4 The Density-matrix and the
Density-operator 20
1.3 Evolution Equations 23
1.3.1 The Interaction Representation 23
1.3.2 Solving the Density-operator
Evolution Equation within the
Bloch–Wangsness–Redfield Theory 24
1.3.3 Evolution Equations of Quantities Associated
with Product-operators 26

vii
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viii Contents
1.4 Spin Relaxation in a Single Spin 1/2 System 28

1.4.1 Relaxation by Random Fields 28
1.4.2 Relaxation by Chemical Shift Anisotropy
(CSA) 29
1.5 Spin Relaxation in a Two Spin 1/2 System Involving

Dipolar Interaction 32
1.5.1 The Dipolar Relaxation Hamiltonian 32
1.5.2 Longitudinal and Transverse
Auto-relaxation Rates Including the Dipolar
Contribution 34
1.5.3 Cross-relaxation Rates 36
1.5.4 Cross-correlation Rates 37
1.6 The Fundamental Relaxation Equations in the Case
of a Two-spin 1/2 System 41
1.6.1 The Nuclear Overhauser Effect (nOe) and the
Simple Solomon Equations 41
1.6.2 The Extended Solomon Equations 45
1.6.3 The Goldman Equations 47
1.7 Multi-spin Systems. Occurrence of Dipolar–Dipolar
Cross-correlation Rates 48
1.7.1 Longitudinal Relaxation 49
1.7.2 Transverse Relaxation 52
1.8 Conclusion 57
.
References 57
Chapter 2 Homonuclear Cross-relaxation and Cross-correlation in

Small Molecules and in Soft Matter 61
Kavita Dorai
2.1 Introduction 61
2.2 One-dimensional Cross-relaxation Experiments in
Homonuclear Systems 62
2.2.1 Steady-state Nuclear Overhauser
Enhancement 62
2.2.2 Transient NOE Experiments 63
2.2.3 2D Cross-relaxation Experiments in
Homonuclear Systems 71
2.2.4 Distance Measurements from NOE
Experiments 77
2.2.5 Selected Examples of the Usefulness of
Cross-relaxation 80
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Contents ix
2.3 Experiments to Measure Cross-correlated

Relaxation Rates 94
2.3.1 Experimental Observation of Longitudinal
Cross-correlations 94
2.3.2 Experimental Observation of Transverse

2.3.3 Cross-correlations Under Spin-lock
Conditions 112
2.3.4 Experimental Dynamic Frequency Shifts 116
2.3.5 Cross-correlations in Paramagnetic and
Quadrupolar Systems 121
2.4 Motional Models and Cross-correlated Spin
Relaxation 125
2.4.1 Spectral Densities for Different Types of
Motion 125
2.4.2 Interpretation of Cross-correlation Motional
Parameters 134
2.5 Molecular Information from Cross-Correlated Spin
Relaxation 135
2.5.1 Structural Parameters from
2.5.2 Estimating the CSA Tensor 136
2.5.3 Information about Carbohydrates and
.
Nucleotides from Cross-correlations 137

2.5.4 Information about Small Ligand
Conformations from Binding Studies using
2.5.5 Motional Information from
Cross-correlation Rates 145
2.6 Conclusions 148
Acknowledgements 149
References 149
Chapter 3 Heteronuclear Cross-relaxation 166

Bernard Ancian
3.1 Introduction and Basic Concepts 166

3.2 The Heteronuclear Overhauser Effect (HOE) 170
3.3 HOE’s Measurements and the Information they
Provide 174
3.4 2D Heteronuclear Overhauser Spectroscopy
(HOESY) 179
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x Contents
3.5 The 1D HOESY Experiment 187

3.6 An Improved HOESY Experiment: The P.HOESY
Sequence 188
3.7 Inverse HOESY Experiments 190
3.8 Filtered-HOESY Experiments 192

3.9 1D HOE and 2D HOESY in Intermolecular
Interactions 193
3.10 Using Intermolecular HOESY in Chemistry and
Biology 198
3.10.1 Chemical Structure, Reactivity and Chiral
Recognition 198
3.10.2 Solute–Solvent Interactions 200
3.10.3 Ion Pairs and Ionic Liquids 206
3.10.4 Metallic Bonds and Aggregates 214
3.10.5 Biology 217
3.11 Conclusion 220
Acknowledgements 221
References 221
Chapter 4 Cross-correlation in Biomolecules 239

Fabien Ferrage and Kavita Dorai
.
4.1 Introduction 239

4.1.1 Definitions 240
4.1.2 Span of Uses 240
4.1.3 Presentation of This Chapter 241
4.2 Theory 241
4.2.1 The Homogeneous Master Equation 241
4.2.2 Frame Transformations of Liouvillian
Superoperators 243
4.2.3 Average Liouvillian Theory: Discrete
Averaging 244
4.2.4 Application of Discrete ALT: Measurement of
CSA/DD CCCR Rates 246
4.2.5 Average Liouvillian Theory: Continuous
Averaging 246
4.2.6 Application of Continuous ALT:
Measurement of CSA/DD CCCR Rates 248
4.2.7 Note on the Secular Approximation 249
4.3 Measurements of Cross-relaxation at the
Steady-state Effects 249
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Contents xi
4.4 HSQC-type Experiments to Measure

Cross-correlated Cross-relaxation Rates 253
4.4.1 Measuring CSA–Dipolar Cross-correlation
(1D Experiments) 253
4.4.2 2D Experiments to Measure CSA–Dipolar

4.4.3 Multi-dimensional Experiments to Measure
Dipole–Dipole Cross-correlations 269
4.4.4 2D Experiments for Measuring CSA–CSA
4.5 Motional Models and Cross-correlated Spin
Relaxation 274
4.5.1 Model-free Formalism and Large
Biomolecules 275
4.5.2 Dipole–Dipole Cross-correlation in
Biomolecules 278
4.5.3 Correlated Internal Motions 280
4.5.4 3D Gaussian Axial Fluctuations Model 281
4.5.5 Extraction of Cross-correlation Parameters
From Dynamics 284
4.5.6 Motional Information From
Cross-correlation Rate 285
4.6 Local Chemical Properties of Biomolecules 286
.
4.6.1 Estimating the CSA Tensor 286

4.6.2 Hydrogen Bonds and Cross-correlated
Cross-relaxation 290
4.7 Chemical Exchange and Cross-correlations 292
4.8 Information About RNA and DNA Nucleic Acids
from Cross-correlations 296
4.9 Ligand-binding Studies Using Cross-correlations 303
4.10 Transverse Relaxation Optimized Spectroscopy:
Tailoring Auto-relaxation with Cross-correlated
Relaxation 304
4.10.1 Interference Between Relaxation
Mechanisms 304
4.10.2 TROSY From CSA–DD Cross-correlated
Relaxation 305
4.10.3 TROSY From DD–DD Cross-correlated
Relaxation 307
References 310
Subject Index 316

.
Published on 09 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782622475-FP007 View Online
Published on 09 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782622475-00001
CHAPTER 1
Introduction to Nuclear
Spin Cross-relaxation and
Cross-correlation Phenomena
in Liquids
DANIEL CANET
Université de Lorraine, France

Email: daniel.canet@univ-lorraine.fr
Nuclear magnetic resonance (NMR) cross-relaxation and cross-correlation

.
phenomena are part of the general nuclear spin relaxation processes. What is
meant by relaxation is very common in physics, chemistry, biochemistry, etc.
and is related to the recovery of a system that has been subjected to different
constraints. As far as NMR is concerned, the nuclear spin system tends to
recover toward its equilibrium configuration, which consists of the so-called
macroscopic magnetization, collinear with the polarizing static magnetic
field B0. This magnetization originates from the magnetic momentum
associated with each spin momentum. A nuclear spin system can be moved
from its equilibrium configuration by changing, non-adiabatically, the B0
field value or, more commonly, by applying pulses of an oscillating magnetic
field called also the radio-frequency field. The latter is generally denoted B1
and, with a frequency close to the nuclear resonances, can induce the NMR
signal. As a matter of fact, the consideration of nuclear spin relaxation was a
key issue for the first NMR experiments.1 Moreover, although the prime

1
View Online
2 Chapter 1
interest of NMR for chemists was its ability to reveal the molecular structure
via chemical shifts and coupling constants, it was rapidly realized that the
relaxation parameters could also provide not only dynamical but structural
information.
Very early (in 1948, whereas the first NMR experiments were performed in
1946), Bloembergen, Purcell and Pound2 were able to interpret the two major
relaxation parameters: T1, the spin–lattice relaxation time (longitudinal
relaxation time), related to the nuclear magnetization component along the
B0 field; and T2, the spin–spin relaxation time (transverse relaxation time),
related to the nuclear magnetization components perpendicular to the
B0 field. These two relaxation times are involved in the famous Bloch
equations3 that, in a phenomenological way, accounts for the evolution
of the three components of the nuclear magnetization (or polarization,
magnetization being the polarization times the gyromagnetic ratio). These
equations are perfectly valid if the system encompasses a single spin species.
However, as soon as one is dealing with a multi-spin system, it is mandatory
to consider a polarization for each spin species and, possibly, further
quantities describing different spin states. Although T1 and T2 remain active
for each individual polarization (they will be referred to as auto-relaxation
parameters), it turns out that all spin states, including the polarization
for each species, may be coupled by various spin relaxation pathways. The
corresponding parameters include the so-called cross-relaxation and cross-
correlation relaxation rates, which are the subject of this book. They arise
from different relaxation mechanisms (considered in Section 1.1) and are
active through the so-called spectral densities, a concept also developed
.
in Section 1.1. How these parameters may be involved in dedicated

experimental procedures is not a simple matter. It requires some know-
ledge of spin quantum mechanics (Section 1.2), which will be used for a
detailed approach of cross-relaxation (Section 1.3) and cross-correlation
(Section 1.4). Finally, the type of molecular information that can be gained
from cross-relaxation and cross-correlation parameters will be surveyed in
Section 1.6.
1.1 A Survey of Nuclear Spin Relaxation Mechanisms

and the Concept of Spectral Densities
One way to perturb a spin system from its equilibrium configuration is
to induce transitions among its energy levels. The same process can be en-
visioned for restoring this equilibrium configuration. Inducing transitions
can be achieved by the application of a radio-frequency field or, without
having recourse to an external constraint, through local fluctuating magnetic
fields. It is the latter that gives rise to relaxation phenomena. Consider, for
simplicity, a single spin 1/2 system, that is a system involving only two
energy levels. In order to induce a transition between these two states, the
experimenter can apply a radio-frequency field at the Larmor frequency n 0
View Online
Nuclear Spin Cross-relaxation and Cross-correlation Phenomena in Liquids 3

ghB0
(or close to this frequency) which is such that: hn 0 ¼ DE ¼ , where DE is
2p
the energy difference between these two energy levels, g the gyromagnetic
ratio of the considered nucleus and h the Planck constant (the shielding
coefficient, responsible for the chemical shift effect, has been omitted). The
constants appearing in the latter expression arise from the relationship

between the magnetic moment and the spin operator I: l ¼ gh I (h stands for
the Planck divided by 2p; with these notations and for a spin 1/2, the length
pffiffiffiffiffiffiffiffi
of the vector I is 3=4 and its projection on a given axis can take the
value þ 12 or 12). However, within a sample, an elementary nuclear magnetic
moment l is subjected to a local magnetic field b(t) originating from the
various interactions to which this magnetic moment is subjected. Due to
molecular motions, this local field is time dependent and consequently
may be able to induce transitions, thus constituting a relaxation mech-
anism. It must however mimic the action of a radio-frequency field and
therefore fulfil the following conditions: (i) present some degree of co-
herence, and (ii) be active at the frequency of the considered transition.
A first global treatment, considering simple randomly fluctuating
magnetic fields (without specifying their characteristics), will be presented
first. Depending on the origin of b(t), specific mechanisms can be considered
and the ones relevant to this book will be detailed thereafter. It can be borne
in mind that each of them will possibly contribute to relaxation rates in an
additive way. The limited relaxation mechanisms treated here are those
which concern spin 1/2 nuclei. For the sake of simplicity, nuclei of spin
greater than 1/2 (also called quadrupolar nuclei) will not be considered,
.
although, in some instances, they could be involved in cross-relaxation and

cross-correlation relaxation rates.
1.1.1 Interaction with Local Randomly Fluctuating Magnetic

Fields
b(t) is, for instance, the magnetic field created by other spins (nuclear spins
or spins of unpaired electrons).4 However, we shall disregard here the origin
of b(t) and just rely on the fact that, due to molecular motions, it randomly
fluctuates (we shall further assume an isotropic medium throughout):
(i) the three components of a local magnetic field (dubbed ‘random

field’ in the following) are not correlated
bx ðtÞby ðtÞ ¼ bx ðtÞbz ðtÞ ¼ by ðtÞbz ðtÞ ¼ 0 (1:1)
(the bar represents an ensemble average)

(ii) the mean value of each component is zero
bx ðtÞ ¼ by ðtÞ ¼ bz ðtÞ ¼ 0 (1:2)

View Online
4 Chapter 1
(iii) the mean value of their squares are identical
b2x ðtÞ ¼ b2y ðtÞ ¼ b2z ðtÞ ¼ b2 (1:3)

To understand the two latter points, one can think of a quantity whose
modulus is non-zero but which can take opposite values with the same
probability.
The coherence of a random field can be evaluated by its correlation
function, i.e.
bx ðtÞbx ð0Þ a 0 (1:4)
which reflects its memory properties. Indeed, if the two quantities are totally
uncorrelated (independent), one has:
bx ðtÞ bx ð0Þ ¼ bx ðtÞ bx ð0Þ ¼ 0 (1:5)
Conversely, a radio-frequency field is totally correlated because it is

represented by a sine (or cosine) function and, consequently, its value at any
time t can be predicted from its value at time zero.
The efficiency of a random field at a given frequency o can be appreciated
by the real part of the Fourier transform of the above correlation function
ð1
Jrf ðoÞ ¼ Re bx ðtÞbx ð0Þ expðiotÞ dt (1:6)
.
(rf ¼ ‘random fields’).

These quantities, of fundamental importance, are called spectral densities
and are involved in all relaxation parameters. Very often bx ðtÞbx ð0Þ can be
written as b2 et=tc , where tc is a correlation time associated with molecular
reorientation (it can be thought as the time required for one radian rotation;
in liquids tc lies generally between 108 and 1012 s). This is especially true
in the case of a sphere, the reorientation of which is governed by the classical
diffusion equation
@c(O,t)/@t ¼ DL c(O,t) (1.7)
Here, c(O,t) is an arbitrary function of the two usual polar angles defining
the sphere orientation (denoted by O) and of time t. L is the angular
Laplacian, while D is the rotational diffusion coefficient:
kB T
D¼ (1:8)
8pa3 Z
(a: sphere radius; kB: Boltzmann constant; T: absolute temperature;

Z: medium viscosity). For many situations encountered here, c(O,t) will be
the spherical harmonics Y20, which is proportional to [3 cos2 y(t) 1], where y
is the angle between a molecular axis (the molecule of interest being a
View Online
sphere) and the B0 direction of the laboratory frame (generally, the

dependence upon a single polar angle stems from the isotropy of the
medium). Upon solving the diffusion equation by means of an expansion
over spherical harmonics,5 one arrives indeed at a solution of the form et/tc
with tc ¼ 1/6D. The Fourier transform of eqn (1.6) yields a Lorentzian
tc
function of the type . More precisely, we shall denote in the
1 þ o2 t2c
following as ‘normalized spectral density’ J~(o) the Fourier transform
pffiffiffiffiffiffiffiffiffiffiffiffiffi
(multiplied by 4p) of the correlation function of Y20 ðyÞ ¼ 5=16pð3 cos2 y 1Þ
ð þ1
~J ðoÞ ¼ Re 8p 0 0
Y2 ½yðtÞY2 ½yð0Þ expðiotÞ dt (1:9a)
0
It can be shown that, for an isotropic medium (exclusively considered in

this chapter), the normalized spectral density is independent of the pro-
jection m of the spherical harmonics Y2m. In a general way, this can be
written as follows (y and j being the classical polar angles)
ð þ1
~J ðoÞ ¼ Re 8p Y2m *½yðtÞY2m ½yð0Þ expðiotÞdt
0
with
Y22 ¼ 15=8pð1=2Þsin2 y expð2ijÞ (1:9b)
.
Y21 ¼ 15=8p sin y cos y expð ijÞ

pffiffiffiffiffiffiffiffiffiffiffiffiffipffiffiffiffiffiffiffiffi
Y20 ¼ 15=8p 3=2 ðcos2 y 1=3Þ
As outlined above, the normalized spectral density is especially simple when

a single correlation time is involved (for instance, when the molecular
reorientation can be approximated by the motion of a sphere, that is an
isotropic motion):
2tc
~J ðoÞ ¼ (1:10)
1 þ o2 t2c
When the condition o2t2c{1 is fulfilled (and this is the case for fast motions
since the NMR measurement frequency is lower than 109 Hz), the spectral
density becomes frequency independent. In such cases, one says that
‘extreme narrowing’ conditions prevail.
It must be mentioned that eqn (1.9a) and (1.9b) refer to an angular
modulation. The molecular motions responsible for such a modulation
are thus purely rotational (often dubbed as ‘reorientational’). Many forms
of spectral densities have been proposed to allow for more complicated
motions. It can be remembered that, as early as 1934, Perrin6 established
and solved the rotational Brownian equations for an ellipsoid. The solution
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6 Chapter 1
involves at most three different diffusion coefficients which lead to appro-

priate spectral densities.7 The superposition of different rotational motions
may lead to very complicated spectral densities. The so-called ‘Lipari–Szabo’
or ‘model-free approach’ or ‘two-step model’ spectral density function8,9 has
gained much popularity because it is consistent with most experimental
determinations and because it involves a minimum set of parameters. In a

working (and simplified) form, this type of spectral density function can be
written as
~J ðoÞ ¼ ð1 S2 Þ2tf þ S2 2ts

(1:11)
1 þ o2 t2s
In eqn (1.11), tf is related to a fast-local motion, assumed to fulfil extreme

narrowing conditions, whereas ts describes a slow overall tumbling. S is a
generalized order parameter which specifies the restriction of the fast local
motion (0rS2r1). Typical applications of eqn (1.11) concerns macromolecules
(slow overall tumbling) involving segmental or rotational isomerism motions
(fast-local motion). This will of course be further discussed in the forthcoming
chapters of this book.
1.1.2 Dipolar Interactions

This terminology10,11 refers to the interaction between the two magnetic
moments l1 and l2 of two distinct spins. It can be noted that, due to aver-
aging by rapid molecular motions in the liquid phase, dipolar interactions
do not lead to any splitting in the NMR spectra. In terms of tensor, this is
.
related to the fact that the trace of the dipolar tensor is zero. To introduce
easily the relevant spectral densities, we shall resort to a simplified treat-
ment and defer to subsequent sections a rigorous quantum mechanical
approach. The classical expression for the dipolar interaction energy is as
follows
3ðl1 rÞðl2 rÞ l1 l2
ED ¼ 3 (1:12)
r5 r
As per Figure 1.1 where the two magnetic moments are parallel to B0 (still a
classical view), eqn (1.11) can be written
m1 m2
ED ¼ ð3 cos2 y 1Þ (1:13)
r3
It should be noted that the same result would be obtained irrespectively of
the magnetic moment orientation (parallel or anti-parallel) with respect to
B0. The two geometrical parameters r and y may be modulated by molecular
motions and thus contribute to nuclear spin relaxation. Indeed, if l1 and l2
belong to two different molecules (inter-molecular dipolar relaxation), the
modulation of both r and y must be considered. The evaluation of the
View Online

Figure 1.1 The various quantities involved in the dipolar interaction between the
two magnetic moments l1 and l2, supposed to be parallel to the static
magnetic field B0.
relevant spectral densities is however somewhat complicated and requires

anyway a model adapted to each situation. Conversely, if l1 and l2 belong to
the same molecule (intra-molecular dipolar relaxation), only the modulation
of y has to be taken into account and one is left with spectral densities in-
volving the quantity (3 cos2 y 1) thus of the type given by eqn (1.9)–(1.11).
Let us recall that, in that case, spin relaxation provides information about
molecular reorientation but also on inter-nuclear distance through the factor
1/r6 appearing necessarily in the correlation function. This point can be
better viewed by expressing eqn (1.13) as a function of the spin operators and
by introducing the spherical harmonics Y20(y). Moreover, consistently with
forthcoming sections, it is useful to express the interaction energy ED in
rad s1 and therefore to divide ED by h .
.
pffiffiffiffiffiffiffiffiffiffiffiffiffi 0
hÞð1=r 3 Þð
ED ¼ ðm0 =4pÞðg1 g2 16p=5ÞY2 ðyÞIz1 Iz2 (1:14)
m0 is the vacuum permeability and the factor (m0/4p) is introduced for unit
compatibility. The spectral density relevant to eqn (1.14) can be written as
KD ~
JD ðoÞ ¼ J ðoÞ (1:15)
r6
where the conventional definition of the coefficient KD has been retrieved
(because one is dealing in this section with a semi-classical theory, the
square of the Iz1Iz2 value had to be inserted in the coefficient of the corre-
lation function):
KD ¼ (1/20)(m0/4p)2(g1g2h
)2 (1.16)
It can be noted that the situation is much more complicated in the

case of inter-molecular dipolar interactions. In addition to rotational
motions which prevail in the case of intra-molecular interactions (as
above), one has, in addition, to deal with translational motions which
modulate the inter-atomic distance r. Such situations will be considered in
Chapter 3.
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8 Chapter 1
1.1.3 Chemical Shift Anisotropy (CSA)

The fact that nuclei of the same isotopic species resonate at specific
frequencies is due to the different environments they undergo (chemical
shifts).10,11 In liquid state NMR, the chemical shift is accounted for by a
screening (or shielding) coefficient which, due to rapid molecular motions,

is in fact the third of the shielding tensor trace. However, at the molecular
level, the shielding tensor must be considered and it is the modulation, by
molecular motions, of its orientation with respect to the laboratory frame
which makes it a possible relaxation mechanism. As for any Cartesian
tensor, it is possible to find out a molecular frame (called the principal axis
system or PAS) in which this tensor is diagonal and to define the orientation
of the PAS (specific of each molecule) with respect to the laboratory frame.
For simplicity, we shall further assume that the shielding tensor is of axial
symmetry and is thus described only by two elements: s8 (corresponding to
the symmetry axis) and s> (corresponding to any axis perpendicular to the
symmetry axis).
This is shown in Figure 1.2 for a given molecule such that the molecular
symmetry axis (denoted by z in the following) makes an angle y with the
laboratory frame axis Z. The Zeeman interaction energy (still expressed in
rad s1) can be written as
EZ ¼gB0(1 sZZ)IZ (1.17)
sZZ being the shielding coefficient along the laboratory frame Z axis. Because
sZZ transforms as Z 2 and that, in the molecular frame, the shielding tensor
is diagonal, one arrives at eqn (1.18), (see Figure 1.2)
.
Ds
sZZ ¼ cos2 y sk þ sin2 y s? ¼ s0 þ ð3 cos2 y 1Þ (1:18)
3
where one has introduced the isotropic shielding coefficient
s0 ¼ (1/3)(s8 þ 2s>) (1.19)
Figure 1.2 The molecular principal axis system of the shielding tensor with respect
to the Z axis (coinciding with the B0 direction) of the laboratory frame.
The shielding tensor is assumed to be axially symmetric, thus involving
only two elements (s8 and s>).
View Online
and the anisotropy of the shielding tensor (also called the chemical shift
anisotropy – CSA)
Ds ¼ s8 s> (1.20)
Ds
It can be seen that ð3 cos2 y 1Þ is the only term in eqn (1.18) which is
3
time dependent. Thus, this relaxation mechanism relies exclusively on
molecular reorientation. Its efficiency depends on the shielding anisotropy
(hence, the acronym CSA) and, of course, on the value of the B0 field.
Therefore, until the advent of high field spectrometers, CSA relaxation was
neglected in proton NMR (the anisotropy of the shielding tensor is assumed
to be very weak). Conversely, unless dealing with a low static magnetic
field, this mechanism had to be considered in the case of carbon-13,
phosphorous-31, nitrogen-15, fluorine-19 etc. To be more specific, the CSA
spectral density can be derived from the Fourier Transform of the correlation
function (as this was done for the dipolar interaction). If (3 cos2 y 1) is
expressed as a function of Y20 (see eqn (1.9a), and similar calculations in the
case of dipolar interactions), this leads to
Jcsa(o) ¼ Kcsa(Ds)2J~(o) (1.21)
with
Kcsa ¼ (1/15)(gB0)2 (1.22)

.
As before, a factor (1/2) has been introduced in eqn (1.22) to account for
the value of IZ in eqn (1.17). In addition, as only one component of the
fluctuating magnetic field is involved in eqn (1.17), a factor of 3 was intro-
duced in eqn (1.22) to account for the three components of the fluctuating
magnetic field. This is because, due an assumed isotropic medium, the
contributions of these three components are identical.
1.1.4 The Spin-rotation Relaxation Mechanism

Although this mechanism10 cannot be involved in cross-relaxation or
cross-correlation relaxation rates, it may contribute to T1 and T2. It arises
from the coupling of two angular momenta, namely the nuclear spin
angular momentum and the molecular rotation angular momentum.
The latter fluctuates with molecular reorientation and is thus prone to
contribute to nuclear spin relaxation. However, this mechanism manifests
itself only in the case of small molecules or for mobile parts of large
molecules (e.g. freely rotating methyl groups). In any event, it has the
particularity (contrary to all other nuclear spin relaxation mechanisms) to
become more efficient when temperature increases and this constitutes a
good means for assessing the presence of a spin-rotation contribution.
View Online
10 Chapter 1
Indeed, a spin-rotation correlation time can be defined and it was shown by

Hubbard12 to be inversely proportional to the rotational correlation time tc
appearing in eqn (1.10).
1.1.5 Correlated Mechanisms

For the sake of simplicity, we shall consider what can be called a relaxation
vector. This is the vector joining the two nuclei for the dipolar mechanism
or the symmetry axis of the shielding tensor for the CSA mechanism. As
shown above, the interaction energy of these two mechanisms involve the
quantity (3 cos2 y 1) where y is the angle between the relaxation vector
and the direction of the static magnetic field. As (3 cos2 y 1) is pro-
portional to the spherical harmonics Y20(y), and as the spectral density
function of eqn (1.9) involves the correlation function Y20 ½yðtÞY20 ½yð0Þ, the
latter will be dubbed an auto-correlation function because it is the same
angle y in both spherical harmonics. However, in the case of two different
relaxation mechanisms, one related to the angle y, the other to the angle y 0 ,
it may happen that the so-called cross-correlation function Y20 ½y0 ðtÞY20 ½yð0Þ
is non-zero because the motions associated with these two mechanisms are
effectively correlated. This will give rise to cross-correlation spectral
densities that, as will be seen later, are prone to couple different spin
states. Cross-correlation may occur every time that the two mechanisms
involve the same spherical harmonics (due to the hypothesis of an isotropic
medium, which will prevail throughout this chapter, it is simply Y20):
dipolar, CSA and even quadrupolar (not considered in this chapter). As an
.
example, the expression of a dipolar-CSA cross-correlation spectral density

is given below
pffiffiffiffiffiffipffiffiffiffiffiffiffiffi Ds
JD;csa ðoÞ ¼ KD Kcsa 3 ~Jcross ðoÞ (1:23)
r
The first interest of such a cross-correlation spectral density lies in its
dependence on 1/r3 and not on 1/r6 in the case of a dipolar auto-correlation
spectral density. It will therefore be more sensitive to the dipolar interaction
between remote nuclei provided, of course, that Ds is large enough. Con-
versely, this property is especially appealing in the case of dipolar–dipolar
cross-correlation spectral densities.
For an isotropic motion (characterized by a single correlation time tc), the
normalized spectral density ~Jcross can be written as
~Jcross ðoÞ ¼ ð1=2Þð3 cos2 a 1Þ 2tc

(1:24)
1 þ o2 t2c
where a is the angle between the two relaxation vectors. Within the frame-
work of the model-free approach, ~Jcross is more complicated13 and requires,
View Online
for each of the two mechanisms, two order parameters S and S 0 (which, to a
first approximation, can be identical):
~Jcross ðoÞ ¼ ½ð1=2Þð3 cos2 a 1Þ SS0 2tf þ SS0 2ts

(1:25)
1 þ o2 t2s
1.2 An Introduction to Spin 1/2 Quantum

Mechanics
As anticipated in the previous section, a classical treatment (or even semi-
classical) will not be appropriate to treat the relatively subtle effects of cross-
relaxation and cross-correlation. Rather, quantum mechanics is inescapable.
Because this chapter is aimed at some self-consistency, the basic features of
spin 1/2 quantum mechanics will be presented.
1.2.1 Operators for a Single Spin 1/2

The quantum mechanical treatment of the magnetic moment l associated
with the spin momentum I(l ¼ gh I, see the introduction to Section 1.1)
implies the definition and properties of spin operators and, at the onset,
their eigenvalues and eigenvectors. Primarily, an operator transforms a
wave-function. Let us recall that, formally, a wave function C defines
through |C| 2 the probability for the system to be in the state associated
with the function C. Concerning spin systems, one has not to worry about
.
this formal statement because wave functions are not analytically known.
Moreover, the situation is very simple in the case of a single spin 1/2 system
since one needs to defined only two basis wave-functions denoted by a
(in this chapter, the notations a, |ai, |1/2i will be equivalent) and b, which
are simply the eigenfunctions (or eigenvectors) of the Îz operator (the
symbol ^ differentiates the operator from its associated quantity).
Îza ¼ (1/2)a Îzb ¼ (1/2)b (1.26)
If the z axis coincides with the direction of the static magnetic field B0,
one recognizes that a corresponds to a magnetic moment parallel to the
magnetic field and b to an anti-parallel orientation. The operator Î 2,
associated with the square of the spin momentum, commutes with the Îz
operator. Two operators are said to commute when they can act one after
the other irrespectively of their order. Concerning the two operators Îz and Î 2,
this means that the product operators ÎzÎ 2 and Î 2Îz act in an identical manner.
Equivalently, using the commutator notation, this can be written
[Îz,Î 2] ¼ ÎzÎ 2 Î 2Îz ¼ 0. Therefore, both operators share the same eigenvectors
Î 2a ¼ (3/4)a Î 2b ¼ (3/4)b (1.27)

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12 Chapter 1
Figure 1.3 Orientations of spin 1/2 magnetic moments in the presence of a static
magnetic field B0.
Eqn (1.26) and (1.27) exemplify the difference between a classical view and
quantum mechanics. Moreover, these relations indicate that the magnetic
moments associated with spin momentums are not aligned with the static
magnetic field (in a parallel or anti-parallel configuration). This illustrated in
Figure 1.3. Magnetic moments are randomly spread over two cones, with,
due to the Boltzmann distribution, a slight excess in the direction of the
static magnetic field (pseudo ‘parallel’ configuration). Only their length and
their projection on the Z axis are known and, contrary to a common belief,
this is not related to some sort of precession phenomenon. Only the
macroscopic nuclear magnetization is subjected to precession.
While Îz can be seen as being associated with the longitudinal com-
.
ponent of nuclear magnetization (along the B0 direction), the two other

operators of interest, namely Îx and Îy, will be associated with the so-called
transverse components which exist only at the condition that the nuclear
magnetization has been removed from its equilibrium configuration (for
instance by a radio-frequency pulse). The action of Îx and Îy is conveniently
treated by the ladder operators: the raising operator Î1 and the lowering
operator Î
Îþ ¼ Îx þ iÎy

(1:28)
Î ¼ Îx iÎy
(with i2 ¼ 1)
It turns out that, in the case of a single spin 1/2, the actions of these ladder
operators are quite simple. One has
Îþ a ¼ 0 Îþ b ¼ a
(1:29)
Î a ¼ b Î b ¼ 0
From eqn (1.28) it is then a simple matter to go back to the action of Îx and Îy.
View Online

2
Îz, Îx and Îy commute separately with Î but do not commute with each other.
The relevant commutators are given below
½Îx ; Îy ¼ iÎz

½Îy ; Îz ¼ iÎx (1:30)
½Îz ; Îx ¼ iÎy
Eqn (1.30) can be complemented by other useful relations, specific to a

spin 1/2
Îx2 ¼ Îy2 ¼ Îz2 ¼ Ê/4 (1.31)
Ê being the identity operator.
ÎxÎy ¼ ÎyÎx ¼ iÎz =2
ÎyÎz ¼ ÎzÎy ¼ iÎx =2 (1:32)
ÎzÎx ¼ ÎxÎz ¼ iÎy =2
The wave-functions (called also vectors) a and b are normalized and orthogonal.
Introducing the scalar product (hbra|keti), this feature is written as
ha|ai ¼ hb|bi ¼ 1
(1:33)
.
ha|bi ¼ hb|ai ¼ 0
The interest of this bra-ket notation (Dirac notation) lies in the possibility to
include the action of a spin operator. This is illustrated by the examples
given below
ha| Îz|ai ¼ 1=2 hb| Îz|bi ¼ 1=2
ha| Îz|bi ¼ 0 hb| Îz|ai ¼ 0

(1:34)
ha|Îþ|bi ¼ 1 hb |Î|ai ¼ 1
:::
In these examples, the operator is considered as acting on the ‘ket’, that is on

the right-hand side vector. If the result is the same when this operator acts
on the ‘bra’, that is on the left-hand side vector, it will be said hermitian. In
fact, all operators associated with a physical quantity are hermitian. This is
the case for Îz, Îx, Îy and Î2. This is not the case for Î1 and Î.
A matrix can be associated with each operator. This matrix is meaningful
if the basis on which it is constructed is specified. The method for con-
structing a matrix associated with an operator is straightforward. The first
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14 Chapter 1
column contains the components (on the chosen basis) of the vector which
results from the action of the considered operator on the first vector of the
chosen basis. The second column is related to the second vector of the
chosen basis and so on.
On the basis (a, b), the matrix associated with Îz and Ê are very simple

1 0 1 0
½Iz ¼ ð1=2Þ ½E ¼ (1:35)
0 1 0 1
The first column of the matrix [I1] has for elements the following scalar
products: ha|Î1|ai ¼ 0 and hb|Î1|ai ¼ 0. Likewise, for the second column, one
has ha|Î1|bi ¼ 1 and hb|Î1|bi ¼ 0. A similar procedure can be applied for
obtaining [I] and these two matrices can be written as

0 1 0 0
½Iþ ¼ ½I ¼ (1:36)
0 0 1 0
From eqn (1.28) and (1.36), it is easy to derive the matrices associated with
Îx and Îy

0 1 0 i
½Ix ¼ ð1=2Þ ½Iy ¼ ð1=2Þ (1:37)
1 0 i 0
where eqn (1.35) and (1.37) are the famous Pauli matrices.
Matrices associated with hermitian operators are said hermitian matrices.
They are equal to their conjugate transpose (also called self-adjoint matrix).
.
As expected, Pauli matrices possess this latter property.

Trace (the sum of diagonal elements) relations will prove very useful. They
can be summarized as follows
Tr(E) ¼ 2 Tr(Iu) ¼ 0 Tr(I2u) ¼ 1/2 Tr(IuIv) ¼ 0 (1.38)
with uav and u,v ¼ x,y or z.

The effect of a radio-frequency field (B1, necessary perpendicular to B0) is
better viewed from the so-called rotating frame. Let (X,Y,Z) the laboratory
frame with Z coinciding with the direction of the static magnetic field B0 and
o the frequency (in rad s1) of the alternating magnetic field B1 used for
inducing the NMR signal. o (also called the carrier frequency) is supposed to
be close to the resonance frequency o0 ¼ gB0(1 s0) for all lines in the
considered spectrum (see eqn (1.19)). The rotating frame (x,y,z Z) is de-
fined as rotating around Z with the angular velocity o, that is in the same
direction as the nuclear precession. It can be shown that the radio-frequency
field appears stationary in this rotating frame if its amplitude is sufficiently
large for avoiding off-resonance effects. B1 is aligned along one the axis of
the (x,y) plane depending on its phase: by convention, it is the x axis for
phase 0. It is the y axis for a phase angle of p/2, the x axis for a phase angle
of p and so on.
View Online

Figure 1.4 Conversion of the Iz state into cosaIz þ sinaIy.
Let t the duration of a radio-frequency pulse and a the so-called flip angle
a ¼ gB1t (1.39)
As for magnetization components, the effect of a radio-frequency pulse on a

spin state represented by one of the three operators Îx, Îy or Îz is just to
‘rotate’ by an angle a (in an anti-clockwise direction) the operator around the
axis along which B1 is stationary. For example, starting from a spin state
represented by Îz and for B1 along x(phase 0), one obtains the following
conversion
ðaÞx
Iz ! cos aIz þ sin aIy (1:40)
This is shown in Figure 1.4 and is illustrated by the two following

.
trivial examples. If a ¼ p/2, the longitudinal spin state Iz is fully transformed

into a transverse spin state (Iy) whereas the transverse spin state Ix remains
unchanged under the (a)x pulse, whatever the value of a.
1.2.2 Product-operators for a System Involving Several

Spins 1/2
To describe the possible spin states of a single spin 1/2, only three operators
(Îz, Îx, Îy) are required plus the identity operator for completing an operator
basis. Indeed, any spin state of a single spin 1/2 can be described by a linear
combination of these three (four) operators. It turns out that the density-
matrix (discussed later) involves (2n2n) elements, n being the number of
spins 1/2 in the considered system. Each element corresponding to a spin
state, this number of elements must be identical to the dimension of the
operator basis. It is possible to construct such a basis (with normalized and
orthogonal elements) by considering all the possible products of operators
of the form
Y
n
^ r ¼ Nr
U ^ðrÞ
S (1:41)
j
j¼1
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16 Chapter 1
with Ŝ(r)
j ¼ Êj, Îxj,
or Îyj Îzj,
the index j labelling one of the spins in the
considered system and Nr being a normalization coefficient which can be
calculated as per the definition of the operator scalar product given below.
As each of these product operators differ from another one by at least one Ŝj,
their number is 4n and they are independent. They are further orthogonal
and normalized as per the following definition of the scalar product

pertaining to operators
Tr(ÛrÛs) ¼ drs (1.42)
where drs is the Kronecker symbol, equal to 1 when r ¼ s and to 0 otherwise.

In eqn (1.42), Ûr should normally be replaced by its self-adjoint which is here
simply Ûr because all these operators are Hermitian. As Ûr and Ûs differ
at least by a spin j 0 if ras and as TrðS ^ðrÞ ^ðsÞ
j 0 Sj 0 ) is zero (see eqn (1.38)),
the orthogonality of these operators is actually verified. Concerning the
normalization coefficient, it can be calculated by the following equation
Y
n
ðrÞ2
^ r2 ¼ Nr2
Tr U ^
TrðS j Þ ¼ Nr2 2er ð1=2Þner (1:43)
j¼1
where er is the number of identity operators in Ûr. Finally, Ûr can be

expressed as
1 Y
n
^r ¼
U ^ðrÞ
S (1:44)
j
2er n=2 j ¼ 1
.
Product-operators, introduced as early as 1983 by Sørensen et al.,14 have proved

invaluable for understanding and analyzing multi-pulse NMR sequences. They
are also convenient for delineating coupling between different spin states
through spin relaxation phenomena.15
1.2.3 Product-operators for a Two Spin 1/2 System and

Relevant Spin States
To gain some physical insight into the above concepts, the simple case of a
two spin 1/2 system will be treated in detail. These two spins will be denoted
A and B. They are supposed to be weakly J-coupled. Moreover, a non-viscous
isotropic medium being assumed, the NMR spectrum consists of two
doublets of splitting J and centered on the resonance frequency of the two
nuclei (denoted n A and n B).
There are 16 product-operators, 15 if the global identity is excluded. In the
following, the identity pertaining to a single spin will be omitted. The
product operators will be classified as per longitudinal spin states, involving
only Îz operators, or to transverse spin states (involving Îx and Îy operators)
called also coherences because they involve a phase coherence created by a
radio frequency field.
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1.2.3.1 Longitudinal Spin States

These include ÎzA and ÎzB. The quantity associated with each of these operators
is often called polarization since it is the equilibrium nuclear magnetization
divided by the gyromagnetic ratio. A third product-operator must be
considered: the so-called longitudinal order represented by 2ÎzAÎzB. The

corresponding quantity can be created by an appropriate pulse sequence
applied to an anti-phase doublet (see below) or, naturally, through relaxation
phenomena involving cross-correlation rates (one of the major subjects of
this book).
1.2.3.2 One Quantum Coherences

The denomination ‘one quantum coherences’ arises from the fact that they
are directly observable. This refers in fact to the basic NMR selection rule: a
transition occurs if, for only one spin, b is changed in a or a in b, these
changes requiring one quantum of energy. The evident corresponding
operators are ÎxA, ÎxB, ÎyA and ÎyB, which are associated with transverse mag-
netization components, the x and y NMR signals differing in phase by p/2.
These are the usual signals with the two doublet lines of the same sign.
Such a doublet will be called in-phase and, for ÎAx, can be sketched by
two arrows (A1 and A2 for the two lines of the A doublet) along the x axis
of the rotating frame (Figure 1.5, left). It can be recalled that each line in the
.
Figure 1.5 Left: an in-phase doublet. Right: an antiphase doublet. Vectors associ-
ated with each line help to understand the product operators associated
with each of these spins states.
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They surprised the dozing cattle, and alarmed astonished sheep,
sent families of grazing rabbits scuttling to their burrows; they heard
the night-jar, the owl, and the corn-crake; bats flapped across their
path, and in narrow lanes the broad shoulders of Wynyard broke the
webs of discomfited spiders. The extraordinary stillness of the night
was what impressed the young man; sometimes, from a distance of
four or five miles, he could hear, with startling distinctness, the
twelve measured strokes of Ottinge church clock.
During these long, aimless rambles, what Joss’ thoughts were, who
can say? Undoubtedly he recalled such excursions in ecstatic
dreams. Wynyard, for his part, took many pleasure trips into the land
of fancy, and there, amidst its picturesque glamour and all its doubts,
distractions, and hopes, his sole companion was Aurea! Nothing but
the hope of her return sustained and kept him day after day, pacing
the Manor yard, in a sense her prisoner! His devotion would have
amazed his sister; she could not have believed that Owen, of all
people, would have been so enslaved by a girl, could have become
a dumb, humble worshipper, satisfied to listen to her laugh, to catch
a radiant glance of her dark eyes, and, when he closed the door of
the car, to shield her dainty skirt with reverent fingers.
Presently there came a spell of bad weather, the rain sweeping
across the country in great grey gusts and eddying whirls, moaning
and howling through the village, making the venerable trees in Mrs.
Hogben’s orchard quite lively in their old age, lashing each other with
their hoary arms, in furious play.
It was impossible for Wynyard to spend the entire evening indoors
over Mrs. Hogben’s fire, listening to tales of when “she was in
service,” though he was interested to hear that Miss Alice Parrett as
was—Mrs. Morven—“was the best of the bunch, and there wasn’t a
dry eye when she was buried.” He also learned that Mr. Morven was
rich for a parson, and had once kept a curate, well paid, too; but the
curate had been terribly in love with Miss Aurea, and of course she
wouldn’t look at him—a little red-haired, rat-faced fellow! and so he
had gone away, and there was no more regular curate, only
weekends, when Mr. Morven went abroad for his holiday. And now
and then Mrs. Hogben would fall into heartrending reminiscences of
her defunct pigs.
“Afore you come, Jack, I kep’ pigs,” she informed him; “one a year. I
bought un at Brodfield—a nice little fellow—for fifteen shillings to a
pound, and fattened un up, being so much alone all day, I could
never help making sort of free with the pig, and petting un. He
always knew me, and would eat out of my hand, and was a sort of
companion, ye see?”
“Yes,” assented Wynyard, though he did not see, for in his mind’s
eye he was contemplating Aurea Morven.
“Well, of course, he grew fat, and ready for the butcher, and when he
was prime, he had to go—but it just broke my heart, so it did; for
nights before I couldn’t sleep for crying,” here she became
lachrymose; “but it had to be, and me bound to be about when the
men came, and the cries and yells of him nigh drove me wild;
though, of course, once he was scalded and hung up, and a fine
weight, it wor a nice thing to have one’s own pork and bacon.”
Her companion nodded sympathetically.
“Howsomever, the last time I was so rarely fond of the pig, and his
screams and carryings-on cut me so cruel, that I made a vow, then
and there, I’d never own another, but take a lodger instead—and
you, Jack, be the first!”
“I’m sure I’m flattered,” rejoined Wynyard, with an irony entirely
wasted on his companion, who, with her skirt turned over her knees,
and her feet generously displayed, sat at the other side of the fire,
thoroughly enjoying herself.
“Tom is out,” he said, and this remark started her at once into
another topic, and a series of bitter complaints of Dilly Topham—
Tom’s girl.
“The worst of it is, she’s mighty pretty, ain’t she?” she asked
querulously.
“She is,” he admitted. Dilly was a round-faced, smiling damsel, with
curly brown hair and expressive blue eyes—a flirt to her finger-tips. It
was also true that she did lead poor Tom a life, and encouraged a
smart young insurance agent, with well-turned, stockinged calves,
and a free-wheel bicycle.
“I’d never put up with her,” declared Mrs. Hogben, “only for her
grandmother.”
“Why her grandmother?” he questioned lazily.
“Bless your dear heart, old Jane Topham has been a miser all her
life. Oh, she’s a masterpiece, she is, and lives on the scrapings of
the shop; she hasn’t had a gown this ten year, but has a fine lump of
money in the Brodfield Bank, and Dilly is all she’s got left, and the
apple of her eye. Dilly will have a big fortune—only for that, I’d put
her to the door, with her giggling and her impudence, yes I would,
and that’s the middle and the two ends of it!”
When Wynyard had heard more than enough of Dilly’s doings and
misdoings, and the biographies and tragedies of his predecessors
(the pigs), he went over to the Drum, listened to discussions, and
realised the prominent characteristics of the English rustic—
reluctance to accept a new idea. Many talked as if the world had not
moved for thirty years, and evinced a dull-witted contentment, a
stolid refusal to look facts in the face; but others, the younger
generation, gave him a new perspective—these read the papers,
debated their contents, and took a keen interest in their own times.
Wynyard generally had a word with old Thunder, and played a game
of chess with Pither, the organist. Captain Ramsay was established
in his usual place—smoking, silent, and staring. So intent was his
gaze, so insistently fixed, that Wynyard invariably arranged to sit with
his back to him, but even then he seemed to feel the piercing eyes
penetrating the middle of his spine!
One evening Captain Ramsay suddenly rose, and shuffled out of his
corner—an usual proceeding, for he remained immovable till closing
time (ten o’clock). He came straight up to where Wynyard was
bending over the chess-board, considering a move, and laying a
heavy hand on his shoulder, and speaking in a husky voice, said—
“I say—Wynyard—don’t you know me?”
CHAPTER XVII
LADY KESTERS HAS MISGIVINGS
At this amazing question the chauffeur started violently, looked up

into the anxious, sunken eyes gazing into his own, and answered—
“No, to the best of my belief, I’ve never seen you before—never till I
came here.”
The man’s worn face worked with violent emotion—which he vainly
struggled to subdue.
“What!” he demanded, in a high, hoarse key, “have you forgotten
Lucknow?—and Jim Ramsay of the Seventh? Impossible!”
Wynyard glanced at him and again shook his head.
After a long pause, expressive of indignant incredulity—
“Why, man alive, you and I were at school together! Don’t you
remember your poky little room over the churchyard, and how we
fagged for Toler, and played hard rackets?”
As Wynyard still remained irresponsive, suddenly, to his horror, the
questioner burst into tears and tottered unsteadily towards the door,
wringing his hands, uttering loud convulsive sobs, and exclaiming,
“As a dead man out of mind! As a dead man out of mind! Tell them to
sound the Last Post!”
There was a loud murmur from the card-players, and old Thunder,
turning about and addressing the company, said—
“Poor old chap, ’e’s worse nor ever. At school together”—to Wynyard
—“Lor’ bless me! why, ye might be his son! I suppose ’e’s a stranger
to ye, mister?”
“Yes; I never laid eyes on him before.”
“He’s a-going off his nut,” declared a voice from the nap table; “he
did ought to be put away—he did.”
“Ay,” agreed the organist, addressing Wynyard, “his good lady won’t
hear of it; but it’s my opinion that he is no longer safe to himself or
others—it’s the loose and at-home lunatics that commit these awful
crimes ye read of in the papers, and makes your blood run cold.”
Wynyard made no reply. He had more than once heard Pither
himself spoken of as a madman and a crazy fellow; but he was
merely eccentric. As for Captain Ramsay, he was lost in conjecture
as to how that unfortunate and afflicted gentleman had got hold of
his real name?
This mystery was solved no later than the next evening. In the lovely,
soft June twilight he was walking past the Claringbold’s empty farm,
and here came upon the captain, who was leaning over the gate,
and signalled imperatively to him with his stick.
“Look here!” he called out, and Wynyard stood still. “You’ve been a
puzzle to me for nearly six weeks—and at last I’ve got you.”
“Got me!”
“Of course you are Owen Wynyard; you and I knew one another long
ago. Why, man! we were schoolfellows, almost like brothers, and
afterwards, when our two regiments lay in Lucknow—why, God bless
me! it’s over thirty years ago!”
Captain Ramsay had got hold of his right name, but otherwise he
was a raving lunatic.
“You are Owen Wynyard, aren’t you?” he asked impatiently.
“Yes, I am, but I don’t use the Wynyard here; and I must beg you to
keep it to yourself.”
“Oh, all right; in one of your old scrapes, my boy! Money scarce! Ha
ha!” and he laughed hysterically. “So you’re lying doggo from the
Soucars, but why here?”
“That’s my business,” he answered sharply.
“Come, come, don’t be so grumpy and short with me, Owen. You
were always such a rare good-tempered chap. What has changed
you, eh? Now, come along home with me, and we will have a good
‘bukh’ over old times,” and, as he spoke, his grasp—a fierce,
possessive clutch—tightened painfully on his prisoner’s arm.
“But,” objected the victim, “I was going for a turn.”
“No, you are not; you are coming straight home with me. My wife will
be glad to make your acquaintance. I forget if you’ve met her?” and
he touched his forehead. “I’m a little funny here, Owen. India, my
boy! she takes it out of all of us one way or another—teeth, hair,
liver, brains. Come on now—right about turn!” he concluded
facetiously.
There was no use in resistance or in having a violent personal
struggle with the lunatic—nothing for it but to submit; and, in spite of
his reluctance, Wynyard was conducted, as if in custody, right up to
the door of Ivy House. Were he to refuse to enter, he knew there
would only be a scene in the street, a gaping crowd, and an
unpleasant exposure.
“Look, look, Tom!” cried Mrs. Hogben, pointing to the opposite
house, “if the captain hasn’t got hold of our young fellow, and a-
walkin’ him home as if he had him in charge—he has took a fancy to
him, I do declare!”
“There’s more nor one has took a fancy to Owen,” remarked Tom,
with gruff significance; “but, as to the captain—well—I’d rather it was
him—nor me.”
The captain entered his house with a latchkey and an air of
importance; there was a light in the square hall, and a door at one
side was ajar. He called out—
“Katie, Katie, come and see what I have found for you!”
A door was opened wide, and there stood Mrs. Ramsay in a tea-
gown, with a little black Pom. in her arms. She looked amazed, as
well she might, but instantly dissembled her surprise, and said—
“Good-evening—I see my husband has invited you in for a smoke?”
“Smoke!” said Captain Ramsay, passing into the drawing-room, and
beckoning Wynyard to follow him. As he did so, he glanced
apologetically at the lady of the house, and it struck him then that he
was looking into a face that had seen all the sorrows of the world.
The room was furnished with solid old furniture, but Mrs. Ramsay’s
taste—or was it Miss Morven’s—had made it a charming and restful
retreat, with pretty, soft wall-paper, rose-shaded lamps, flowers, a
quantity of books, and a few Indian relics—such as a brass table, a
phoolcarrie or two, and some painted Tillah work which he
recognised as made near Lucknow.
“Katie,” resumed her husband, after a pause, “I know you will be
pleased to hear I’ve met a very old friend,” and he laid his hand
heavily on Wynyard’s shoulder. “Let me introduce Captain Wynyard
—Owen Wynyard of the Red Hussars. He and I were quartered
together in Lucknow, a matter of thirty-three years ago—why, I knew
him, my dear, long before I ever set eyes on you!”
As he concluded, he gazed at her with his dark shifty eyes, and
Wynyard noticed the nervous twitching of his hands.
“I’m sure I’m delighted to make your acquaintance,” she said, with
the utmost composure, though her lips were livid. Jim was getting
worse—this scene marked a new phase of his illness—another
milestone on the road to dementia.
“We were inseparable, Katie, I can tell you, and went up together for
our leave to Naini Tal, and stayed at the club, rowed in the regatta,
had a ripping time, and went shooting in Kumaon. I say, Owen, do
you remember the panther that took your dog near Bhim Tal—and
how you got him?”
Wynyard nodded assent—in for a penny, in for a pound! He was
impersonating a dead man, and what was a dead dog more or less?
“Do you remember the cairn we raised over him, and he was so
popular, every one who knew him, that passed up or down, placed a
stone on it?”
“Wouldn’t you like to go and smoke in the dining-room?” suggested
Mrs. Ramsay. “Jim, I’ll ring for Mary to light the lamp, she does not
know you are in.”
“No, no, I’ll go myself,” and he shuffled into the hall.
“He has taken you for some one else, of course, poor fellow!” she
said, turning quickly to Wynyard, and speaking under her breath.
“Yes,” he answered, “for my father—but please keep this to yourself
—I’ve always heard I am extraordinarily like him.”
“Then humour him, humour him, do. You see how bright and happy
this imaginary meeting has made him. Oh, it will be so kind of you to
talk to him of India—he loves it—how I wish you knew the country—
you must pretend, and I will coach you. Lucknow is very hot, and
gay, not far——”
“But I needn’t pretend,” he broke in, “I know the country—yes—and
Lucknow too. I was there with my father’s old regiment.”
She stared at him for a moment in bewildered astonishment.
“I say, you won’t give me away, will you?” he added anxiously.
“No; is it likely? If you will only come and talk to him of an evening
now and then, it will be truly one of the good deeds that will be
scored up to you in heaven. Ah, here he is, and the lamp.”
“Now come along, Owen,” he said briskly. “Here you are, I’ve got my
best tobacco for you. Let’s have a bukh!”
And what a bukh it was! Captain Ramsay carried on most of the
conversation, and as he discoursed of old friends, of shikar, of
camps and manœuvres, racing and polo, his sunken eyes kindled,
he became animated; it was another personality to that of the silent,
drooping figure known to Ottinge. Wynyard, as he listened and threw
in a word or two, could now dimly realise the good-looking smart
officer in this poor stranded wreck.
Mrs. Ramsay, who had brought her work and her little dog, sat
somewhat apart, beyond the shaded lamp’s rays, listened,
wondered, and inwardly wept. What vital touch to a deadened mind
had kindled these old memories? What a mysterious organ was the
human brain!
And the taciturn chauffeur, he too was changed—it was another
individual; he sat there, smoking, his elbow on the table, discussing
army matters (now obsolete), notable generals, long dead and gone,
the hills and plains of India, the climate—that, at least, was
unchanged—with extraordinary coolness and adaptability. The guest
was playing the rôle of being his own father, with astounding
success. And what a good-looking young fellow! she noticed his
clear-cut features, the well set-on head, the fine frame, the
distinguished looking brown hand that lay carelessly on the table.
The scene was altogether amazing; this sudden recognition seemed
to have aroused Jim from a long, long mental slumber. Was it a sign
of recovery—or was it a symptom of the end?
When at last Owen rose to go, Captain Ramsay made no effort to
detain him, but sat, with his head thrown back and his eyes fixed on
the opposite wall, lost in a reverie of ghastly vacuity.
It was Mrs. Ramsay who accompanied her guest into the hall, and
inquired, in her everyday manner—
“And when is the motor of Ottinge coming back?”
“I am to fetch it to-morrow.”
Then, in another voice, almost a whisper, she added—
“I am so grateful to you. My husband and your father seem to have
been like brothers—and you really managed wonderfully. You have
given Jim such pleasure, and, poor fellow, he has so little!” Her eyes
were dim as she looked up, “Even I, who am with him always, see a
change. I am afraid he is growing worse.”
“Why not better?” asked Wynyard, with forced cheerfulness. “Have
you seen a mental specialist?”
“Oh yes, long ago; his condition is the result of sunstroke, and they
said he—he ought to be—put away in an asylum; but of course his
home is his asylum.”
Her visitor was not so clear about this, and there was no doubt that
now and then the captain’s eyes had an alarmingly mad expression.
“Can you manage to come and see him occasionally, or is it asking
too much?”
“I’ll come with pleasure; I have my evenings off—the car never goes
out at night, as you may know; but I’m only Owen Wynyard, late of
the Red Hussars, in this house, if you please, Mrs. Ramsay.”
“Of course; and I shall be only too thankful to see you whenever you
can spare us an hour,” and she opened the door and let him out.
From this time forth there commenced an intimacy between the
chauffeur and the Ramsays. He not only spent an hour now and then
with the captain, smoking, playing picquet, and talking over old
times, but he gave Mrs. Ramsay valuable assistance with her
boarders, treated bites, thorns, and other casualties with a practised
hand; on one occasion sat up at night with a serious case of
distemper; on another, traced and captured a valuable runaway. He
admired her for her unquenchable spirit, energy, and pluck, and
helped in the kennel with the boy she employed, and undertook to
exercise the most boisterous dogs of an evening. These thoroughly
enjoyed their excursions with an active companion, who, however,
maintained a strict but kindly discipline; and, of a bright moonlight
night, it was no uncommon sight to meet the chauffeur, four or five
miles from Ottinge, accompanied by, not only Joss, but by several of
Mrs. Ramsay’s paying guests.
The friendship between the captain and the chauffeur naturally did
not pass unnoticed, and the verdict of the Drum was that the young
fellow, having spare time on his hands, had been “took on as a sort
of keeper at Ivy House, and gave a help with the kennel and the old
man—and the old man was growing worse.”
Leila had arranged to pay a flying visit to Brodfield when her brother
went there to fetch the motor, and he found her awaiting him in a
gloomy sitting-room of that once celebrated posting-inn—the Coach
and Horses.
“Three months are gone!” she said, after their first greetings, “so far
so good, ce n’est que le premier pas qui coute!”
“There are a good many pas yet! It’s awfully nice to see you, Sis,
and be myself for once in a way,” and then he proceeded to unfold
his experience with Captain Ramsay.
“Oh, how ghastly! The poor lunatic talking away to you, and taking
you for our father! Imagine him recognising you by the likeness, and
skipping thirty-three years! No one else suspects you, do they?”
“His wife knows my real name, and that’s all; I had to tell her, but she
is safe as a church. Miss Susan has been curious.”
“Bless her dear simple heart!”
“I say amen to that; but of all the mean, purse-proud, tyrannical old
hags, give me Bella Parrett! She’s always bragging of her family, too,
and her crest—in my opinion it ought to be a civet cat!”
“Oh, Owen,” and she laughed, “it’s not often that you are stirred to
such indignation.”
“Ah, you don’t know her.”
“Apparently not. Well, what do you say to a move, and to better
yourself? I believe I could find you a capital place in Somersetshire,
not so retired, more in the world, and with quite smart people.”
“No, thanks, I’ll stick to this now—anyway till Christmas.”
“But, Owen, when the old woman and the motor are so objectionable
—by the way, I must inspect it before you start to-morrow—why
remain?”
“Oh, I’ve got the hang of the place now. I know the people, I’ve
comfortable quarters—and—er—I like Miss Susan——”
“Do you like any one else, Owen, come?”
“I like the parson, and the schoolmaster, and Tom Hogben.”
“Well, well, well!” throwing herself back, “I see you won’t give me
your confidence! I am positively certain there is some one in Ottinge
you like much better than the parson and the schoolmaster—or even
Miss Susan.”
“I swear there is not,” he answered, boldly confronting her. (Aurea
was not in Ottinge, but visiting her rich London relatives, doing a bit
of the season with, to borrow the native term, “Mrs. General
Morven.”)
Leila was puzzled. Owen, she knew, was a hopelessly bad liar, and
his face looked innocence itself.
“I’ve got a box for the theatre here—a company on tour. We may as
well go—you can sit in the back,” she said, rising.
“All right; it’s to be hoped none of the Ottinge folk will be there, and
spot me!”
“Not they! Don’t you know your Ottinge by this time? Is it likely that
any one of them would come all this way to see a mere play?”
“Miss Susan might, she loves an outing and any little bit of
amusement; but she’s not at home, and if she was, she would not
get the use of the motor.”
“The theatre is only across the square—it’s quite near, so we may as
well walk;” and they did. Lady Kesters in a high black dress, her
brother in a dark suit, passed unnoticed among the crowd, and
enjoyed the entertainment.
The next morning Lady Kesters left Brodfield by the ten o’clock train
for London, having previously inspected the celebrated green gem at
the garage. She even got into it, examined it critically, and laughed
as she descended.
“Oh, what a take in! What a shame to have cheated those poor old
women! Why, Owen, I believe it must be years and years old!”
“And a bad machine always; strong when you want it to be weak,
and weak when it should be strong. Some of these days it will play
me a trick, I’m sure.”
“What, that old bone-shaker! No, no. Well, I’m afraid you must soon
be starting—as you say Miss Parrett awaits you, watch in hand—and
so must I. It’s been awfully good to see you, and find you are getting
on so well—‘a chauffeur almost to the manner born.’ Martin takes a
profound interest in our enterprise.”
“He keeps me supplied with lots of tobacco and A1 cigars. Tell him
that Miss Susan asked me if I got them in the village? and Miss
Parrett, who is as sharp as a razor, inquired how I could afford to buy
them? I ventured to offer a couple to the doctor—I told him they were
a present; he took them like a lamb, and asked no questions.”
“What! does a lamb smoke? Well, I’ll tell Martin how much his
offerings are appreciated, and that you really are fit—and quite
happy, eh?”
“Yes, tell him that neither of you need worry about me; I’m all right at
Ottinge.”
But when, an hour later, Lady Kesters gazed meditatively on the
flying Midlands, with her thoughts concentrated upon her brother,
she was by no means so sure, that he was all right at Ottinge!
CHAPTER XVIII
THE REASON WHY
Whilst Ottinge had been dozing through lovely summer days, Aurea
Morven was enjoying a certain amount of the gay London season.
General and Mrs. Morven had no family—Aurea was their only
young relative, the Parretts’ only niece, the parson’s only child; and,
though she was the light of the Rectory, he was not selfish, and
shared and spared her company. Besides, as Mrs. Morven said,
“Edgar had his literary work, his large correspondence, his parish,
and Jane Norris to look after him, and it was out of the question to
suppose that a girl with such beauty and attractiveness was to be
buried in an out-of-the-way hole like Ottinge-in-the-Marsh—although
her father and her aunts did live there!” Mrs. Morven, a masterful
lady on a large scale, who carried herself with conscious dignity,
looked, and was a manager—a manager of ability. She was proud of
the general’s pretty niece, enjoyed chaperoning her and taking her
about, and anticipated her making a notable match; for, besides her
pretty face, and charming, unspoiled nature, Aurea was something of
an heiress.
It seemed to this clear-sighted lady that her niece was changed of
late, her spontaneous gaiety had evaporated, once or twice she had
sudden fits of silence and abstraction, and, although she laughed
and danced and appeared to enjoy herself, refused to take any of
her partners seriously, and shortened her visit by three weeks!
Miss Susan had arrived at Eaton Place for a couple of days. It was
arranged by the girl that she and her aunt were to leave town
together—though the general and his wife pleaded for a longer visit,
offering Aurea, as a temptation, a ball, a Windsor garden-party, and
Sandown—the filial daughter shook her head, with smiling decision;
she had promised the Padre, and, besides, she wanted to get back
to the garden before the best of the roses were over! Theatre
dinners were breaking up at the Ritz, and a stream of smart people
were gradually departing eastward. Among the crowd in the hall,
awaiting her motor, stood Lady Kesters, superb in diamonds and
opera mantle. She and Miss Susan caught sight of one another at
the same moment, and Miss Susan immediately began to make her
way through the throng.
“So glad to meet you!” gasped the elder lady. “I called yesterday
afternoon, but you were out.”
“Yes, so sorry—I was down in the country. Do come and lunch to-
morrow.”
“I wish I could, but, unfortunately, we are going home. Let me
introduce my niece, Aurea Morven—Lady Kesters.”
Lady Kesters smiled and held out her hand. Could this extremely
pretty girl be the reason of Owen’s surprising contentment? She
looked at her critically. No country mouse, this! her air and her frock
were of the town. What a charming face and marvellous complexion
—possibly due to the Marsh air!
“I have known your aunts for years”; and, though addressing Miss
Susan, she looked straight at Aurea, as she asked, “And how is the
new chauffeur suiting you?”
The girl’s colour instantly rose, but before she could speak, Miss
Susan flung herself on the question.
“Oh, very well indeed—most obliging and civil—has been quite a
treasure in the house and garden.”
Lady Kesters raised her delicately pencilled eyebrows and laughed.
“The chauffeur—gardening! How funny!”
“You see, Bella is so nervous in a motor, it is not often wanted, and
Owen likes to help us. We find him rather silent and reserved about
himself; he gives the impression of being a bit above his place?” and
she looked at Lady Kesters interrogatively.
“Really?”
“I suppose you can tell me something about him—as you said you’d
known him for years?” continued Miss Susan, with unconcealed
eagerness. “I am, I must confess, just a little curious. Where does he
come from? Has he any belongings?”
“Oh, my dear lady, do you think it necessary to look into your
chauffeur’s past! I believe he comes from Westshire, his people—er
—er—lived on my grandfather’s property; as to his belongings—ah!
there is my husband! I see he has found the car at last, and I must
fly! So sorry you are leaving town to-morrow—good-bye!” Lady
Kesters now understood her brother’s reluctance to leave Ottinge—
she had seen the reason why.
Miss Susan and her niece travelled down to Catsfield together, were
met in state by the motor and luggage-cart, and created quite a stir
at the little station. Miss Morven had such a heap of boxes—one as
big as a sheep trough—that the cart was delayed for nearly a quarter
of an hour, and Peter, the porter, for once had a job:
The ladies found that, in their absence, the neighbourhood had
awakened; there were large house-parties at Westmere and
Tynflete, and not a few smart motors now to be seen skimming
through the village. It was a fact that several tourists had visited the
church, and had “tea” at Mrs. Pither’s, and patronised her
neighbour’s “cut flowers.” The old church was full on Sundays,
dances and cricket matches were in prospect, and Miss Morven, the
countryside beauty, was immediately in enviable request.
Miss Parrett had relaxed her hold, so to speak, upon the car, and
lent it daily, and even nightly, to her niece and sister; indeed, it
seemed that she would almost do anything with the motor than use it
herself; and though she occasionally ventured to return calls at a
short distance, it was undoubtedly pain and grief to her to do so—
and, on these occasions, brandy and heart-drops were invariably
secreted in one of its many pockets.
Owen, the automaton chauffeur, was the reluctant witness of the
many attentions showered upon his lady-love, especially by Bertie
Woolcock, who was almost always in close attendance, and put her
in the car with many voluble regrets and urgent arrangements for
future meetings. He would linger by the door sometimes for ten
minutes, prolonging the “sweet sorrow,” paying clumsy compliments,
and making notes of future engagements upon his broad linen cuff.
He little suspected how dearly the impassive driver longed to
descend from his seat and throttle him; but once he did remark to the
lady—
“I say, what a scowling brute you have for a chauffeur!”
Meanwhile, Miss Susan looked on and listened to Bertie’s speeches
with happy complacency. Bertie was heir to twenty thousand a year,
and it would be delightful to have her darling Aurea living at
Westmere, and established so near home.
One evening, returning from a garden-party, Miss Susan and her
niece had a narrow escape of being killed. Aurea was seated in front
—she disliked the stuffy interior, especially this warm weather; they
had come to a red triangle notice, “Dangerous to Cyclists,” and were
about to descend a long winding hill—the one hill of the
neighbourhood. Just as they commenced the descent with the brake
hard on, it suddenly broke, and in half a second the car had shot
away!
Wynyard turned his head, and shouted, “Sit tight!” and gave all his
mind to steering; he took the whole width of the road to get round the
first corner, and then the hill made an even sharper drop; the car,
which was heavy, gathered momentum with every yard, and it
seemed impossible to reach the bottom of the hill without some
terrible catastrophe. Half-way down was another motor. Wynyard
yelled, sounded the horn, and flashed by; a pony-trap, ascending,
had a narrow escape of being pulverised in the green car’s mad
flight. Then, to the driver’s horror, he saw a great wagon and horses
on the road near the foot of the hill, and turned cold with the thought
that there might not be room to get by. They missed it by a hair’s-
breadth, and continued their wild career. At last they came to the
level at the foot of the slope, and Wynyard pulled up, after the most
exciting two minutes he had ever experienced. He glanced at his two
companions; they were both as white as death—and so was he!
Miss Susan, for once, was speechless, but at last she signed that

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Cross relaxation and cross correlation

parameters in NMR molecular

Cross Disciplinary Cross Institutional Collaboration in

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New Developments in NMR

Titles in the Series:

and Heterogeneous Materials

How to obtain future titles on publication:

For further information please contact:

New Developments in NMR No. 12

Print ISBN: 978-1-84973-913-9

r The Royal Society of Chemistry 2018

All rights reserved

The Royal Society of Chemistry is a charity, registered in England and Wales,

For further information see our web site at www.rsc.org

nuclear Overhauser eﬀect (nOe), which generated a new era in nuclear

New Developments in NMR No. 12

cross-relaxation and cross-correlation. The next two chapters are devoted to

covered all theoretical, conceptual and experimental aspects of this still

Chapter 1 Introduction to Nuclear Spin Cross-relaxation and

1.1 A Survey of Nuclear Spin Relaxation Mechanisms

1.2.1 Operators for a Single Spin 1/2 11

New Developments in NMR No. 12

1.4 Spin Relaxation in a Single Spin 1/2 System 28

1.5 Spin Relaxation in a Two Spin 1/2 System Involving

Chapter 2 Homonuclear Cross-relaxation and Cross-correlation in

2.3 Experiments to Measure Cross-correlated

2.3.2 Experimental Observation of Transverse

Nucleotides from Cross-correlations 137

Chapter 3 Heteronuclear Cross-relaxation 166

3.1 Introduction and Basic Concepts 166

3.5 The 1D HOESY Experiment 187

3.8 Filtered-HOESY Experiments 192

Chapter 4 Cross-correlation in Biomolecules 239

4.1 Introduction 239

4.4 HSQC-type Experiments to Measure

4.4.2 2D Experiments to Measure CSA–Dipolar

4.6.1 Estimating the CSA Tensor 286

Subject Index 316

Université de Lorraine, France

Nuclear magnetic resonance (NMR) cross-relaxation and cross-correlation

New Developments in NMR No. 12

in Section 1.1. How these parameters may be involved in dedicated

1.1 A Survey of Nuclear Spin Relaxation Mechanisms

Nuclear Spin Cross-relaxation and Cross-correlation Phenomena in Liquids 3

constants appearing in the latter expression arise from the relationship

although, in some instances, they could be involved in cross-relaxation and

1.1.1 Interaction with Local Randomly Fluctuating Magnetic

(i) the three components of a local magnetic field (dubbed ‘random

bx ðtÞby ðtÞ ¼ bx ðtÞbz ðtÞ ¼ by ðtÞbz ðtÞ ¼ 0 (1:1)

(the bar represents an ensemble average)

bx ðtÞ ¼ by ðtÞ ¼ bz ðtÞ ¼ 0 (1:2)

(iii) the mean value of their squares are identical

b2x ðtÞ ¼ b2y ðtÞ ¼ b2z ðtÞ ¼ b2 (1:3)

bx ðtÞbx ð0Þ a 0 (1:4)

bx ðtÞ bx ð0Þ ¼ bx ðtÞ bx ð0Þ ¼ 0 (1:5)

Conversely, a radio-frequency field is totally correlated because it is

Y21 ¼ 15=8p sin y cos y expð ijÞ