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Density Matrix
and
Product Operator
Treatment
Gheorghe D. Mateescu
and
Adrian Valeriu
Department of Chemistry
Case Western Reserve University
Cleveland, Ohio
To the memory of our teachers and parents
Contents
Foreword x
Preface xi
Acknowledgements xiii
Part I. The Density Matrix Formalism
1. Introduction 1
2. The Density Matrix 1
3. The Density Matrix Description of a TwoDimensional
Heteronuclear Correlation Sequence (2DHETCOR) 4
3.1 Calculation Steps 4
3.2 Equilibrium Populations 5
3.3 The First Pulse 7
3.4 Evolution from t(1) to t(2) 9
3.5 The Second Pulse 10
3.6 Evolution from t(3) to t(4) 11
3.7 The Role of '
1
11
3.8 Third and Fourth Pulses 13
3.9 The Role of '
2
14
3.10 Detection 16
3.11 Comparison of the DM Treatment with Vector
Representation 21
4. The Density Matrix Description of a DoubleQuantum
Coherence Experiment (INADEQUATE) 31
4.1 Equilibrium Populations 32
4.2 The First Pulse 34
4.3 Evolution from t(1) to t(2) 35
4.4 The Second Pulse 37
4.5 Evolution from t(3) to t(4) 38
4.6 The Third Pulse 39
4.7 Evolution from t(5) to t(6) 39
4.8 The Fourth Pulse 40
4.9 Detection 42
4.10 CarbonCarbon Connectivity 43
v
vi Contents
5. Density Matrix Description of COSY (Homonuclear
COrrelation SpectroscopY) 45
5.1 Equilibrium Populations 45
5.2 The First Pulse 46
5.3 Evolution from t(1) to t(2) 46
5.4 The Second Pulse 46
5.5 Detection 49
6. COSY with Phase Cycling 52
6.1 Comparison with the Previous Sequence 52
6.2 The Second Pulse 53
6.3 Detection 57
7 Conclusion of Part I 59
Part II. The Product Operator Formalism
1. Introduction 60
2. Expressing the Density Matrix in Terms of
Angular Momentum Components 60
3. Describing the Effect of a Pulse inTerms of
Angular Momenta 62
4. An Unsuccessful Attempt to Describe a Coupled
Evolution in Terms of Angular Momenta 65
5 Product Operators (PO) 67
6. Pulse Effects (Rotations) in the Product
Operator Formalism 70
7. Treatment of Evolutions in the Product
Operator Formalism 74
8. Refocusing Routines 77
Contents vii
9. PO Treatment of 2DHETCOR: Two Spins (CH) 80
10. PO Treatment of 2DHETCOR: CH
2
and CH
3
83
11. PO Treatment of a Polarization Transfer Sequence:
INEPT (Insensitive Nuclei Enhancement by
Polarization Transfer) with Decoupling 87
12. Coupled INEPT 89
13. PO Treatment of DEPT (Distortionless
Enhancement Polarization Transfer) 94
14. PO Treatment of APT (Attached Proton Test) 102
Appendices
A. Math Reminder 105
B. Density Matrix Formalism 120
C. Angular Momentum and Rotation Operators 137
D. Properties of Product Operators 147
E. Demonstration of the Rotation Rules 159
F. Demonstration of the Coupled Evolution Rules 163
G. PO Evolution Tables 169
H. Demonstration of the Refocusing Rules 171
I. Supplementary Discussions 174
J. Product Operators and Magnetization Components 180
K. When to Drop Nonobservable Terms (NOT) 183
L. Magnetic Equivalence: The Multiplet Formalism 184
M. Rotations about Nontrivial Axes 188
Suggested Readings 192
Index 193
Foreword
There is hardly any doubt that NMR is nowadays the
most powerful and perhaps also the most beautiful analytical
technique. Its versatility and its range of applications is truly
unlimited.
NMR is unique in the sense that it derives its power
largely from a quantum mechanical understanding of its
foundations. Those who master a mathematical description
of NMR experiments have an enormous advantage over users
who blindly follow the rules of the instruction manuals.
The most elegant, most simple, and also most intuitive
description developed so far is the product operator formal
ism that is the central subject treated in this book. This
formalism is like a magic key that provides access to the
enormous arsenal of NMR techniques available today and
permits the user to select and properly apply the most suited
tools as well as to develop himself novel, perhaps even more
useful, techniques.
I am convinced that this pedagogically very well done
book by Gheorghe D. Mateescu and Adrian Valeriu will
serve its purpose exceptionally well in the hands of numerous
novices that intend to enter this fascinating field of science.
Richard R. Ernst
Asilomar, April 1992
viii
Preface
Until recently, the teaching and understanding of modern
(pulse) Nuclear Magnetic Resonance has made successful use of
vector descriptions, including handwaving, since the pulse sequences
were relatively simple. The advent of twodimensional NMR made it
practically impossible to explain the intricate effects of combined
pulses and evolutions exclusively on the basis of vector representa
tion. It thus became necessary to use an appropriate tool, the density
matrix (DM) formalism. The DM treatment is generally found in
specialized books which emphasize its quantum mechanical founda
tion. The quantum mechanical approach, however, constitutes a
significant barrier for a growing number of students and scientists in
the fields of chemistry, biology, medicine and materials research who
want to gain a better understanding of 2D NMR.
This book constitutes a guide for the use of density matrix
calculations in the description of multipulse NMR experiments. In
keeping with its didactic nature, the text follows a stepbystep proce
dure which contains more detail than usual. This will give readers
with modest mathematical background the possibility to work out or
to create sequences of various degrees of complexity. Our treatment
begins with an intuitive representation of the density matrix and
continues with matrix calculations without trying to explain the
quantum mechanical origin of pulse effects (rotations) and evolution
of the matrix elements. The quantum mechanical approach is deferred
to Appendix B. Those who do not want to take anything for granted
may actually begin with Appendix B (it is assumed, of course, that the
reader is familiar with the principles and experimental aspects of
Fourier transform NMR).
The first part of the book contains a detailed DM description of
the popular twodimensional sequence, 2DHETCOR (2D heteronu
clear correlation). It starts with the characterization of the system of
nuclei at equilibrium in a magnetic field and concludes with the
calculated signal which results from application of pulses and
evolutions. This section is written in such a way as to be accessible to
students with only an undergraduate mathematical background (there
is even a Math Reminder in Appendix A). In order to ensure the
continous flow of the minimal information needed to understand the
sequence without too many sidetracks a number of detailed
calculations of secondary importance are given in Appendix I.
ix
x Preface
x
Once familiar with 2DHETCOR, the student is led, stepby
step, through the calculations of a doublequantum coherence se
quence and those of the widely used COSY (correlation spectros
copy). Throughout this book we did not use the t
1
and t
2
notations for
the two time variables in a 2D experiment.in order to avoid confusion
with the relaxation times T
1
and T
2
. Also, there is still no consensus
as to what notation should be given to the detection period (some call
it t
1
, some t
2
).
The second part is entirely dedicated to the product operator
(PO) formalism. The student will appreciate the significant economy
of time provided by this elegant condensation of the density matrix
procedure. He or she will be able to handle in reasonable time and
space systems of more than two nuclei which would require much
more elaborate calculations via the unabridged DM treatment.
Appendix B offers an accessible quantum mechanical presenta
tion of the density matrix. Appendix C contains a selection of angular
momenta and rotation operators written in matrix form, while
Appendix D summarizes the properties of product operators.
Appendices E through M are for students interested in a
demonstration of the relations and procedures used in the text.
Throughout the book, relaxation processes have been neglected;
this does not affect the essential features of the calculated 2D spectra
and contributes to the clarity of the presentation.
The teaching method presented in this book has been
successfully used in an Instrumental Analytical Chemistry graduate
course for the past few years at Case Western Reserve and in several
short courses. Being essentially a selfsufficient teaching tool (lecture
notes), this book does not contain literature references. Numerous
citations can be found in the books indicated in the Suggested
Readings section. One of us being a passionate skier, we may say our
class is for beginners, Farrar and Harriman's, for intermediates, and
ErnstBodenhausenWokaun's, for advanced. In fact, our work is a
synergic complement to Martin and Zektzer's TwoDimensional NMR
Methods for Establishing Molecular Connectivity: A Chemist's Guide
to Experiment Selection, Performance, and Interpretation.
Acknowledgments
We thank Guy Pouzard and Larry Werbelow of the Université
de Provence (Marseille) for stimulating discussions which inspired our
endeavor. The first presentations of our way of teaching the density
matrix formalism was at two NATO Advanced Study Institutes
organized in 1983 by Camille Sandorfy and Theophile Theophanides
in Italy and by Leonidas Petrakis and Jacques Fraissard in Greece.
We thank for permission to use material from those papers, published
by D. Reidel Publishing Company (listed in the Suggested Reading
Section). We also thank Frank Anet of UCLA and Gary Martin of the
Burroughs Welcome Co. for their comments and encouragement. Our
publishing team has done an excellent job and we wish to thank
Sidney Solomon and Raymond Solomon of the Solomon Press, Betty
Sun of Prentice Hall, and the wonderful copyeditor Mary Russell.
Last, but not least, we acknowledge the loving care and understanding
of our spouses, Claudia and Anca.
xi
1
The Density Matrix Formalism
1. INTRODUCTION
Only the simplest NMR pulse sequences can be properly
described and understood with the help of the vector representation
(or handwaving) alone. All twodimensional experiments require the
density matrix formalism. Even some onedimensional NMR
sequences (see Part II.12) defy the vector treatment because this
approach cannot account for the polarization transfer. The goal of
Part I is to show how the density matrix can be used to understand a
specific NMR pulse sequence. A "math reminder" is given in
Appendix A for those who may need it. After becoming familiar with
the use of the density matrix as a tool, the reader may find enough
motivation to go to Appendix B which deals with the quantum
mechanical meaning of the density matrix.
2. THE DENSITY MATRIX
Before entering the formal treatment of the density matrix (see
Appendix B) let us build an intuitive picture. We begin with the
simple system of two spin 1/2 nuclei, A and X, with its four energy
levels E
1
to E
4
(Figure I.1) generally described in introductory NMR
textbooks. We assume here (and throughout the book) a negative
gyromagnetic ratio, ̤ This explains the spin angular momentum
orientation against the field in the lowest energy level E
4
. Of course,
in this state the magnetic moment is oriented with the field.
1
2 Density Matrix Treatment
+1
0
0
( )
( )
( )
( )
m A X
E
E
E
E
1
2
3
4
A
Q
X
Q
A
Q
X
Q
A
Q + J/2
X
Q + J/2
A
Q  J/2
X
Q  J/2
1
Figure I.1. Energy levels of an uncoupled (left) and coupled (right)
heteronuclear AX system. The first column contains the total
magnetic quantum number, m. Transition (precession) frequencies Q
A
andQ
X
and the coupling constant J are expressed in Hz.
The possible connections between the four quantum states
represented by the "kets"
, , , ,
are shown in Table I.1 (we assign the first symbol in the ket to nucleus
A and the second, to nucleus X).
This is the general form of the density matrix for the system
shown in Figure I.1. It can be seen that the offdiagonal elements of
the matrix connect pairs of different states. These matrix elements are
called "coherences" (for a formal definition see Appendix B) and are
labeled according to the nature of the transitions between the
corresponding states. For instance, in the transition
only the nucleus A is flipped. The corresponding matrix element will
represent a single quantum coherence implying an A transition and
will be labeled 1Q
A
. We thus find two 1Q
A
and two 1Q
X
coherences
(the matrix elements on the other side of the diagonal do not represent
other coherences; they are mirror images of the ones indicated above
the diagonal). There is also one doublequantum coherence, 2Q
AX
,
Introduction to Density Matrix 3
related to the transition
o .
The zeroquantum coherence ZQ
AX
can be considered as
representing a flipflop transition E
2
E
3
. The name of this coherence
does not necessarily imply that the energy of the transition is zero.
The diagonal elements represent populations.
Table I.1. Translation of the Classical Representation of
a Twospin System into a Density Matrix Representation
AX
P 1 Q 1 Q 2 Q
P ZQ 1 Q
P 1 Q
P
1 A X
2 AX
3 A
4
AX
X
The density matrix contains complete information about the
status of the ensemble of spins at a given time. Populations and
macroscopic magnetizations can be derived from the elements of the
density matrix, as we will see later. The reciprocal statement is not
true: given the magnetization components and populations we do not
have enough information to write all the elements of the density
matrix. The extra information contained in the density matrix enables
us to understand the NMR sequences which cannot be fully described
by vector treatment.
4 Density Matrix Treatment
3. THE DENSITY MATRIX DESCRIPTION OF
A TWODIMENSIONAL HETERONUCLEAR
CORRELATION SEQUENCE (2DHETCOR)
The purpose of 2DHETCOR is to reveal the pairwise correla
tion of different nuclear species (e.g., CH or CF) in a molecule. This
is based on the scalar coupling interaction between the two spins.
3.1 Calculation Steps
Figure I.2 reveals that the density matrix treatment of a pulse
sequence must include the following calculation steps:
 thermal equilibrium populations (off diagonal elements are
zero)
 effects of rf pulses (rotation operators)
 evolution between pulses
 evolution during acquisition
 determination of observable magnetization.
Applying the sequence to an AX system (nucleus A is a
13
C,
nucleus X is a proton) we will describe in detail each of these steps.
t
d
t(0) t(1) t(4) t(6) t(7)
90xH
t(2) t(3)
180xC
Decouple H
C
13
1
t(5)
90xC
/2
e
t /2
e
t
' '
1 2
t(8) t(9)
90xH
Figure I.2. The twodimensional heteronuclear correlation sequence:
90xH t
e
/2 180xC t
e
/2 A
1
90xH 90xC A
2
AT.
2DHETCOR 5
3.2 Equilibrium Populations
At thermal equilibrium the four energy levels shown in Figure
I.1 are populated according to the Boltzmann distribution law:
exp( / )
exp
exp( / )
j i
i i
j j
E E
P E kT
P E kT kT
÷
÷
= =
÷
(I.1)
Taking the least populated level as reference we have:
2 1 1 2
/ exp[( ) / ] exp[ ( / 2) / ]
A
P P E E kT h J kT v = ÷ = + (I.2)
Since transition frequencies (10
8
Hz) are more than six orders of
magnitude larger than coupling constants (tens or hundreds of Hz), we
may neglect the latter (only when we calculate relative populations; of
course, they will not be neglected when calculating transition frequen
cies). Furthermore, the ratios hv
A
/kT and hv
X
/kT are much smaller
than 1. For instance, in a 4.7 Tesla magnet the
13
C Larmor frequency
is v
A
= 50 x 10
6
Hz and
34 6 1
5
23
6.6 10 Js 50 10 s
0.785 10
1.4 10 (J/K) 300K
A
h
p
kT
v
÷ ÷
÷
÷
= = =
This justifies a first order series expansion [see (A11)]:
2 1
/ exp( / ) 1 ( / ) 1
A A
P P h kT h kT p v v = ~ + = + (I.3)
3 1
/ exp( / ) 1 ( / ) 1
X X
P P h kT h kT q v v = ~ + = + (I.4)
4 1
/ 1 [ ( ) / ] 1
A X
P P h kT p q v v ~ + + = + + (I.5)
In the particular case of the carbonproton system the Larmor
frequencies are in the ratio 1:4 (i.e., q = 4p).
We now normalize the sum of populations:
6 Density Matrix Treatment
1 1
P P =
2 1
(1 ) P p P = +
3 1
(1 4 ) P p P = +
4 1
(1 5 ) P p P = +
____________________
1 1
(I.6) 1 (4 10 ) P p PS = + =
Hence,
1
1/ P S =
2
(1 ) / P p S = +
3
(1 4 ) / P p S = +
4
(1 5 ) / P p S = +
where 4 10 S p = +
Given the small value of p we can work with the approximation
S#4. Then the density matrix at equilibrium is:
( )
1
2
3
4
0 0 0 1 0 0 0
0 0 0 0 1 0 0
1
0
0 0 0 0 0 1 4 0 4
0 0 0 0 0 0 1 5
P
P p
D
P p
P p
(
(
+
(
= =
( +
(
+
¸ ¸ ¸
(
(
(
(
(
¸
1 0 0 0 0 0 0 0
0 1 0 0 0 1 0 0
1
0 0 1 0 0 0 4 0 4 4
0 0 0 1 0 0 0 5
p
(
(
(
= +
(
(
¸ ¸ ¸
(
(
(
(
(
¸
It is seen that the first term of the sum above is very large
compared to the second term. However, the first term is not important
since it contains the unit matrix [see (A20)(A21)] and is not affected
by any evolution operator (see Appendix B). Though much smaller, it
is the second term which counts because it contains the population
differences (Vive la difference!). From now on we will work with this
2DHETCOR 7
term only, ignoring the constant factor p/4 and taking the license to
continue to call it D(0):
0 0 0 0
0 1 0 0
(0)
0 0 4 0
(I.7)
0 0 0 5
D
(
(
(
=
(
(
¸ ¸
Equilibrium density matrices for systems other than CH can be built
in exactly the same way.
3.3 The First Pulse
At time t(0) a 90
o
proton pulse is applied along the xaxis. We
now want to calculate D(1), the density matrix after the pulse. The
standard formula for this operation,
D(1) = R
1
D(0) R, (I.8)
is explained in Appendix B. The rotation operator, R, for this
particular case is [see (C18)]:
90
1 0 0
0 1 0
1
(I.9)
0 1 0
2
0 0 1
xH
i
i
R
i
i
(
(
(
=
(
(
¸ ¸
where i is the imaginary unit. 1
Its inverse (reciprocal), R
1
, is readily calculated by
transposition and conjugation [see (A22)(A23)]:
1
90
1 0 0
0 1 0
1
(I.10)
0 1 0
2
0 0 1
xH
i
i
R
i
i
÷
÷ (
(
÷
(
=
( ÷
(
÷
¸ ¸
First we multiply D(0) by R. Since the matrix multiplication is not
commutative (see Appendix A for matrix multiplication rules), it is
necessary to specify that we postmultiply D(0) by R:
8 Density Matrix Treatment
0 0 0 0 1 0 0
0 1 0 0 0 1 0
1
(0)
0 0 4 0 0 1 0
2
0 0 0 5 0 0 1
i
i
D R
i
i
(
(
(
=
(
(
¸ ¸ ¸
(
(
(
(
(
¸
0 0 0 0
0 1 0
1
4 0 4 0
2
(I.11)
0 5 0 5
i
i
i
(
(
(
=
(
(
¸ ¸
Then we premultiply the result by R
1
:
1
1 0 0 0 0 0 0
0 1 0 0 1 0
1 1
(1) [ (0) ]
0 1 0 4 0 4 0
2 2
0 0 1 0 5 0
i
i i
D R D R
i i
i i
÷
÷
5
( (
(
÷
(
(
= =
(
( ÷ (
(
÷
(
¸ ¸ ¸ ¸
4 0 4 0 2 0 2 0
0 6 0 4 0 3 0 2
1
(I.12)
4 0 4 0 2 0 2 0 2
0 4 0 6 0 2 0 3
i i
i i
i i
i i
÷ ÷ ( (
( (
÷ ÷
( (
= =
( (
( (
¸ ¸ ¸ ¸
It is good to check this result by making sure that the matrix
D(1) is Hermitian, i.e., every matrix element below the main diagonal
is the complex conjugate of its corresponding element above the
diagonal [see (A24)] (neither the rotation operators, nor the partial
results need be Hermitian). Comparing D(1) to D(0) we see that the
90
o
proton pulse created proton singlequantum coherences, did not
touch the carbon, and redistributed the populations.
2DHETCOR 9
3.4 Evolution from t (1) to t (2)
The standard formula
1
describing the time evolution of the
density matrix elements in the absence of a pulse is:
( ) (0) exp( )
mn mn mn
d t d i t e = ÷ (I.13)
d
mn
is the matrix element (row m, column n) and Z
mn
=(E
m
E
n
)/= is
the angular frequency of the transition mn.
We observe that during evolution the diagonal elements are
invariant since exp[i(E
m
E
m
)/= ] = 1. The off diagonal elements
experience a periodic evolution. Note that d
mn
(0) is the starting point
of the evolution immediately after a given pulse. In the present case,
the elements d
mn
(0) are those of D(1).
We now want to calculate D(2) at the time t(2) shown in Figure
I.2. We have to consider the evolution of elements d
13
and d
24.
In a
frame rotating with the proton transmitter frequency Z
trH
, after an
evolution time t
e
/2, their values are:
13 13
2 exp( / 2)
e
d i i t B = ÷ ÷ O = (I.14)
24 24
2 exp( / 2)
e
d i i t C = ÷ ÷ O = (I.15)
where :
13 13
Z Z
trH
and :
24 24
Z Z
trH
.
Hence
2 0 0
0 3 0
(2)
* 0 2 0
(I.16)
0 * 0 3
B
C
D
B
C
(
(
(
=
(
(
¸ ¸
B* and C* are the complex conjugates of B and C (see Appendix A).
1
In our treatment, relaxation during the pulse sequence is ignored. This
contributes to a significant simplification of the calculations without
affecting the main features of the resulting 2D spectrum.
10 Density Matrix Treatment
3.5 The Second Pulse
The rotation operators for this pulse are [see(C17)]:
1
180 180
0 0 0 0 0 0
0 0 0 0 0 0
(I.17); (I.18)
0 0 0 0 0 0
0 0 0 0 0 0
xC xC
i i
i i
R R
i i
i i
÷
÷ ( (
( (
÷
( (
= =
( ( ÷
( (
÷
¸ ¸ ¸ ¸
Postmultiplying D(2) by R gives:
180
0 2 0
3 0 0
(2) (I.19)
0 * 2
* 0 3 0
xC
i iB
i iC
D R
i iB i
iC i
(
(
(
=
(
(
¸ ¸
Premultiplying (I.19) by R
1
gives:
3 0 0
0 2 0
(3) (I.20)
* 0 3 0
0 * 0 2
C
B
D
C
B
(
(
(
=
(
(
¸ ¸
Comparing D(3) with D(2) we note that the 180
o
pulse on carbon has
caused a population inversion (interchange of d
11
and d
22
). It has also
interchanged the coherences B and C (d
13
and d
24
). This means that
B, after having evolved with the frequency e
13
during the first half
of the evolution time [see (I.14)], will now evolve with the frequency
e
24
, while C switches form e
24
to e
13
.
2DHETCOR 11
3.6 Evolution from t (3) to t (4)
According to (I.13) the elements d
13
and d
42
become:
d C
13 13
exp( / 2)
e
i t = ÷ O (I.21)
d B
24 24
exp( / 2)
e
i t = ÷ O (I.22)
From Figure I.1 we see that in the laboratory frame
13
2 ( / 2)
X H
J J e t v e t = ÷ = + (I.23)
24
2 ( / 2)
X H
J J e t v e t = ÷ = ÷ (I.24)
In the rotating frame (low case) Z becomes (capital) :. Taking the
expressions of B and C from (I.14) and (I.15), relations (I.21) and
(I.22) become
13
2 exp[ ( ) / 2]exp[ ( ) / 2]
H e H e
d i i J t i J t t t = ÷ ÷ O ÷ ÷ O +
2 exp( )
H e
i i = ÷ ÷ O t
d
(I.25)
(I.26)
24 13
2 exp( )
H e
d i i t = ÷ ÷ O =
None of the matrix elements of D(4) contains the coupling
constant J. The result looks like that of a decoupled evolution. The
averaged shift :
+
(center frequency of the doublet) is expressed while
the coupling is not. We know that the coupling J was actually present
during the evolution, as documented by the intermediate results D(2)
and D(3). We call the sequence t
e
/2  180C  t
e
/2 a refocusing routine.
The protons which were fast (:
13
) during the first t
e
/2 are slow (:
24
)
during the second t
e
/2 and vice versa (they change label).
3.7 The Role of '
1
In order to understand the role of the supplementary evolution
'
1
we have to carry on the calculations without it, i.e., with d
13
=d
24
.
We find out (see Appendix I) that the useful signal is canceled. To
obtain maximum signal, d
13
and d
24
must be equal but of opposite
signs. This is what the delay '
1
enables us to achieve.
12 Density Matrix Treatment
Evolution during '
1
yields:
d d i
13 13 13 1
5 4 ( ) ( ) exp( ) ÷ O A
÷ ÷ ÷ + 2
1
i i t i J
H e H
exp( ) exp[ ( ) ] O O A r (I.27)
÷ ÷ + ÷ 2
1 1
i i t i J
H e
exp[ ( )]exp( ) O A A r
d i i t i J
H e 24 1 1
5 2 ( ) exp[ ( )]exp( ) ÷ ÷ + + O A A r (I.28)
To achieve our goal we choose '
1
=1/2J, which implies rJ'
1
=r/2.
Using the expression [see (A16)]
exp( / ) cos( / ) sin( / ) ± ± i i ±i r r r 2 2 2
exp( ) ÷ i ÷ J i r A
1
(I.29)
exp( ) + i + J i r A
1
We now have
d i t
H e 13 1
5 2 ( ) exp[ ( )] ÷ ÷ + O A
(I.30)
d i t
H e 24 1
5 2 ( ) exp[ ( )] + ÷ + O A
For the following calculations it is convenient to use the notations
c t
H e
+ cos[ ( )] O A
1
(I.31)
s t
H e
+ sin[ ( )] O A
1
which lead to
d c is
is
13
5 2 ( ) ( ) ÷ ÷
(I.32)
d c
24
5 2 ( ) ( ) + ÷
2DHETCOR 13
At this point the density matrix is:
(I.33)
3 0 2( ) 0
0 2 0 2(
(5)
2( ) 0 3 0
0 2( ) 0 2
c is
c is
D
c is
c is
ª º
« »
« »
« »
« »
¬ ¼
)
3.8 Third and Fourth Pulses
Although physically these pulses are applied separately, we
may save some calculation effort by treating them as a single
nonselective pulse.
The expressions of R
90xC
and R
90xH
are taken from Appendix C.
R R R
xCH xC xH 90 90 90
1 0 0 1 0
1 0 0 0 1 0
1 1
0 0 1 0 1 0
2 2
0 0 1 0 0 1
i i
i i
i i
i i
ª º ª º
« » « »
« » « »
« » « »
« » « »
¬ ¼ ¬ ¼
0
1 1
1 1
1
1 1 2
(I.34)
1 1
i i
i i
i i
i i
ª º
« »
« »
« »
« »
¬ ¼
The reciprocal of (I.34) is:
1
90
1 1
1 1
1
1 1 2
1 1
xCH
i i
i i
R
i i
i i
ª º
« »
« »
« »
« »
¬ ¼
14 Density Matrix Treatment
D R
xCH
( ) 5
90
3 2 ( ) 3 2( ) 3 2( ) 3 2 (
2 2( ) 2 2 ( ) 2 2 ( ) 2 2( )
1
3 2( ) 3 2 ( ) 3 2 ( ) 3 2( ) 2
2 2 ( ) 2 2( ) 2 2( ) 2 2 ( )
i c is i c is i c is i c is
i c is i c is i c is i c is
i c is i c is i c is i c is
i c is i c is i c is i c is
ª º
« »
« »
« »
« »
¬ ¼
)
Premultiplying the last result by R gives
xCH 90
1 ÷
5 4 0 4
4 5 4 0
1
(7)
0 4 5 4 2
(I.35)
4 0 4 5
i is ic
i is ic
D
ic i is
ic i is
ª º
« »
« »
« »
« »
¬ ¼
Comparing D(7) with D(5) we make two distinct observations. First,
as expected, carbon coherences are created in d
12
and d
34
due to the
90xC pulse. Second, the proton information [s = sin:
H
(t
e
+ '
1
)] has
been transferred from d
13
and d
24
into the carbon coherences d
12
and
d
34
, which are
d
i i
12
4
2
÷ s
d
i i
34
4
2
+ s
This is an important point of the sequence because now the mixed
carbon and proton information can be carried into the final FID.
3.9 The Role of A
2
As we will see soon, the observable signal is proportional to the
sum d
12
+ d
34
. If we started the decoupled acquisition right at t(7), the
terms containing s would be cancelled. To save them, we allow for
one more short coupled evolution '
2
. Since no r.f. pulse follows after
t(7), we know that every matrix element will evolve in its own box
according to (I.13). It is therefore sufficient, from now on, to follow
the evolution of the carbon coherences d
12
and d
34
which constitute the
observables in this sequence.
2DHETCOR 15
According to (I.13), at t(8) coherences d
12
and d
34
become
d i s i
12 12 2
8 1 2 2 ( ) ( / ) exp( ) ÷ ÷ O A (I.36)
d i s i
34 2
8 1 2 2
34
( ) ( / ) exp ( ) + ÷ O A (I.37)
where :
12
= u
12
u
trC
and :
34
= u
34
u
trC
indicate that now we are
in the carbon rotating frame, which is necessary to describe the carbon
signal during the free induction decay.
÷ ÷
As shown in Figure I.1 the transition frequencies of carbon (nu
cleus A) are:
v v v
v v v
12
34
2 2
2 2
+ +
÷ ÷
A C
A C
J J
J J
Since Z = 2SQ, and we are in rotating coordinates we obtain:
O O
12
+
C
J r (I.38)
O O
34
÷
C
J r (I.39)
Hence,
d i s i i J
C 12 2 2
8 1 2 2 ( ) ( / ) exp( ) exp( ) ÷ ÷ ÷ O A A r (I.40)
d i s i i J
C 34 2 2
8 1 2 2 ( ) ( / ) exp( ) exp( ) + ÷ + O A A r (I.41)
Analyzing the role of '
2
in (I.40 41) we see that for '
2
= 0
the terms in s which contain the proton information are lost when we
calculate the sum of d
12
and d
34
As discussed previously for '
1
, here
also, the desired signal is best obtained for '
2
= 1/2J, which leads to
exp(±irJ'
2
) = ±i and
÷
d s i
C 12 2
8 1 2 2 ( ) ( / ) exp( ) + ÷ ÷ O A (I.42)
d s i
C 34 2
8 1 2 2 ( ) ( / ) exp( ) ÷ + ÷ O A (I.43)
16 Density Matrix Treatment
3.10 Detection
From the time t(8), on the system is proton decoupled, i.e., both
d
12
and d
34
evolve with the frequency :
C
:
d s i i t
C C d 12 2
9 1 2 2 ( ) ( / ) exp( ) exp( ) + ÷ ÷ ÷ O A O (I.44)
d s i i t
C C d 34 2
9 1 2 2 ( ) ( / ) exp( ) exp( ) ÷ + ÷ ÷ O A O (I.45)
Our density matrix calculations, carried out for every step of the
sequence, have brought us to the relations (I.4445). Now it is time to
derive the observable (transverse) carbon magnetization components.
This is done by using the relations (B19) and (B20) in Appendix B:
(I.46) M M iM M p d d
TC xC yC oC
+ ÷ + ( / )(
* *
4
12 34
)
The transverse magnetization M
T
is a complex quantity which com
bines the x and y components of the magnetization vector. We must
now reintroduce the factor p/4 which we omitted, for convenience,
starting with (I.7). This allows us to rewrite (I.46) into a simpler
form:
M M d d
TC oC
÷ + (
* *
12 34
) (I.47)
By inserting (I.4445) into (I.47) we obtain
M M s i i
T
t
C oC C C d
4
2
exp( ) exp( ) O A O (I.48)
With the explicit expression of s (I.31):
M M t i i
T
t
C oC H e C C d
+ 4
1 2
sin[ ( )]exp( ) exp( ) O A O A O (I.49)
Equation (I.49) represents the final result of our 2DHETCOR
analysis by means of the density matrix formalism and it contains all
the information we need.
We learn from (I.49) that the carbon magnetization rotates by
:
C
t
d
while being amplitude modulated by the proton evolution :
H
t
e
.
Fourier transformation with respect to both time domains will yield
the twodimensional spectrum.
The signal is enhanced by a factor of four, representing the
H
/y
C
ratio. The polarization transfer achieved in 2DHETCOR and y
2DHETCOR 17
other heteronuclear pulse sequences cannot be explained by the
vector representation.
When transforming with respect to t
d
, all factors other than
exp(i:
C
t
d
) are regarded as constant. A single peak frequency, :
C
, is
obtained. When transforming with respect to t
e
, all factors other than
sin[:
H
(t
e
+ '
1
)] are regarded as constant. Since
sino
o o
÷
÷
e e
i
i i
2
(I.50)
both +O
H
and ÷O
H
are obtained (Figure I.3a).
C C C
H
O
÷O
H
H
0
O
C
(a)
H
O
C
13
O
24
O
13
÷O
24
÷O
0
(b)
H
12
O
34
O
13
O
24
O
13
÷O
24
÷O
0
(c)
Figure I.3. Schematic 2D heteronuclear correlation spectra (contour
plot): (a) fully decoupled, (b) proton decoupled during the acquisition,
and (c) fully coupled. Filled and open circles represent positive and
negative peaks. With the usually employed magnitude calculation
(absolute value), all peaks are positive. See experimental spectra in
figures 3.11, 3.9 and 3.7 of the book by Martin and Zektzer (see
Suggested Readings).
Imagine now that in the sequence shown in Figure I.2 we did
not apply the 180
o
pulse on carbon and suppressed A
1
. During the
evolution time t
e
the proton is coupled to carbon. During the
18 Density Matrix Treatment
acquisition, the carbon is decoupled from proton. The result (see
Appendix I) is that along the carbon axis we see a single peak, while
along the proton axis we see a doublet due to the protoncarbon
coupling. If we calculate the magnetization following the procedure
shown before, we find:
M M t t i t
TC oC e e C d
÷ ÷ + 2
13 13 2
(cos cos ) exp[ ( )] O O O A (I.51)
Reasoning as for (I.49) we can explain the spectrum shown in Figure
I.3b.
Finally, if we also suppress the decoupling during the acquisi
tion and the delay '
2
we obtain (see Appendix I)
M iM t t i t
TC oC e e d
÷ ÷ + ( / cos cos ) exp( ) 1 2
13 24 12
O O O
÷ + ÷ iM t t i t
oC e e d
( / cos cos ) exp( ) 1 2
13 24 34
O O O (I.52)
which yields the spectrum shown in Figure I.3c.
The lower part of the spectra is not displayed by the instrument,
but proper care must be taken to place the proton transmitter beyond
the proton spectrum. Such a requirement is not imposed on the carbon
transmitter, provided quadrature phase detection is used.
The peaks in the lower part of the contour plot (negative proton
frequencies) can also be eliminated if a more sophisticated pulse se
quence is used, involving phase cycling. If such a pulse sequence is
used, the proton transmitter can be positioned at midspectrum as well.
An example of achieving quadrature detection in the domain t
e
is
given in Section 6 (COSY with phase cycling).
So far we have treated the AX (CH) system. In reality, the pro
ton may be coupled to one or several other protons. In the sequence
shown in Figure I.2 there is no protonproton decoupling. The 2D
spectrum will therefore exhibit single resonances along the carbon
axis, but multiplets corresponding to protonproton coupling, along
the proton axis. An example is given in Figure I.4a which represents
the high field region of the 2DHECTOR spectrum of a molecule
2DHETCOR 19
F
i
g
u
r
e
I
.
4
a
.
T
h
e
h
i
g
h
f
i
e
l
d
r
e
g
i
o
n
o
f
t
h
e
2
D
H
E
T
C
O
R
s
t
a
c
k
p
l
o
t
o
f
a
N
e
n
i
t
z
e
s
c
u
’
s
h
y
d
r
o
c
a
r
b
o
n
d
e
r
i
v
a
t
i
v
e
i
n
C
D
C
l
3
(
a
t
5
0
M
H
z
f
o
r
1
3
C
)
.
T
h
e
p
e
a
k
s
c
o
r
r
e
s
p
o
n
d
i
n
g
t
o
t
h
e
c
a
r
b
o
n
y
l
s
,
t
h
e
m
e
t
h
y
l
g
r
o
u
p
,
a
n
d
t
h
e
c
a
r
b
o
n
i
n
p
o
s
i
t
i
o
n
9
a
r
e
a
t
l
o
w
e
r
f
i
e
l
d
s
(
M
.
A
v
r
a
m
,
G
.
D
.
M
a
t
e
e
s
c
u
a
n
d
C
.
D
.
N
e
n
i
t
z
e
s
c
u
,
u
n
p
u
b
l
i
s
h
e
d
w
o
r
k
)
.
20 Density Matrix Treatment
Figure I.4b. Contour plot of the spectrum in Figure I.4a.
formally derived from [4,2,2,0
2,5
]deca3,7,9triene (Nenitzescu's
hydrocarbon). The delays A
1
and A
2
were set to 3.6 ms in order to optimize
the signals due to
1
J (e140 Hz). It should be noted that the relation (I.49)
has been derived with the assumption that A
1
= A
2
= A = 1/2J. For any other
values of J the signal intensity is proportional to sin
2
rJA. Thus, signals
coming from long range couplings will have very small intensities. Figure
I.4b is a contour plot of the spectrum shown in Figure I.4a. It shows in a
more dramatic manner the advantage of 2D spectroscopy: the carbonproton
correlation and the disentangling of the heavily overlapping proton signals.
2DHETCOR 21
3.11 Comparison of the DM Treatment with Vector
Representation
It is now possible to follow the 2DHETCOR vector representa
tion (Figures I.6a through I.6d) and identify each step with the
corresponding density matrix. It will be seen that one cannot draw the
vectors for the entire sequence without the knowledge of the DM
results.
As demonstrated in Appendix B (see B15B22) the magnetiza
tion components at any time are given by:
M M p d d d d
zA oA
( / )( ) 2
11 22 33 44
(B15)
M M q d d d d
zX oX
( / )( ) 2
11 33 22 44
(B21)
(B20)
M M p d
TA oA
( / )(
* *
4
12 34
d )
d M M q d
TX oX
( / )(
* *
4
13 24
)
(B22)
Considering the simplification we made in (I.7), we must multiply the
expressions above with the factor p/4. Also, remembering that for the
CH system q = 4p, we obtain
M M d d d d
zC oC
( / )( ) 2
11 22 33 44
M M d d d d
zH oH
( / )( ) 8
11 33 22 44
M M d d
TC oC
(
* *
12 34
)
)
(I.53)
M M d d
TH oH
( / )(
* *
4
13 24
We will use the relations (I.53) throughout the sequence in order to
find the magnetization components from the matrix elements.
At time t(0) the net magnetization is in the zdirection for both
proton and carbon. Indeed, with the matrix elements of D(0) (see I.7)
we find
M M M
zC oC oC
( / )( ) 2 0 1 4 5
M M M
zH oH oH
( / )( ) 8 0 4 1 5
(I.54)
The transverse magnetizations M
TC
and M
TH
are both zero (all off
diagonal elements are zero), consistent with the fact that no pulse has
been applied.
22 Density Matrix Treatment
Although they are indiscernible at thermal equilibrium, we will
now define fast and slow components using Figure I.5.
E
E
E
E
1
2
3
4
A
Q
X
Q
A
Q
X
Q
A
Q + J/2
X
Q + J/2
A
Q  J/2
X
Q  J/2
( )
( )
( )
( )
C H C H
f f
f s
s f
s s
Figure I.5. Fast and slow labeling.
It is seen that protons in states 1 and 3 cannot be involved but in the
higher frequency transition 1 3, i.e., they are fast. Those in states 2
and 4 are slow. Likewise, carbons in states 1 and 2 are fast, those in
states 3 and 4 are slow. Therefore, according to (I.53) and (I.54), at
t(0) half of M
zH
is due to fast protons (d
11
d
33
) and the other half to
slow protons. The fast and slow components of the proton
magnetization are marked in Figure I.6 with 13 and 24, respectively.
For carbon, it is 12 and 34.
Speaking of CH pairs, a proton can add or subtract to the field
"seen" by the carbon. Therefore the carbon will be fast if it pairs with
a spinup proton or slow if it pairs with a spindown proton. The
carbon spins will have a similar effect on protons. Figure I.5 shows
that the spins become faster or slower by J/2 Hz.
Immediately after the 90xH pulse proton coherences were
created. Using the matrix elements of D(1) (see I.12) we obtain:
M M i i iM
TH oH oH
( / )( ) 4 2 2
2DHETCOR 23
This tells us that the pulse brought the proton magnetization on the
yaxis (the reader is reminded that in the transverse magnetization,
M
T
= M
x
+ iM
y
, the real part represents vectors along the xaxis and the
imaginary part vectors along the yaxis). It can be verified that the
longitudinal proton magnetization is zero since d
11
d
22
+d
33
d
44
=
(cf I.53). The carbon magnetization was not
affected [Figure I.6a t(1)].
2 2 3 3 0
The chemical shift evolution :
H
t
e
/2 is the average of the fast
and slow evolutions discussed above [see (I.23 24)]. The vector 13
is ahead by +SJt
e
/2, while 24 is lagging by the same angle (i.e.,
SJt
e
/2). The DM results [see (I.14 16)] demonstrate the same
thing:
M M B C
TH oH
( / )( * *) 4
( / )[ exp( / ) exp( / )] M i i t i i t
oH e e
4 2 2 2 2
13 24
: :
i M i t i Jt i Jt
oH H e e
(
e
/ ) exp( / )[exp( / ) exp( / )] 4 2 2 : 2 S S
The carbon is still not affected [Figure I.6a t(2)].
Figure I.6b t(3) tells us that the 180xC pulse reverses the carbon
magnetization and also reverses the proton labels. As discussed
above, the protons coupled to up carbons are fast and those coupled to
down carbons are slow. Therefore inverting carbon orientation results
in changing fast protons into slow protons and vice versa. This is
mathematically documented in the DM treatment [see (I.20)]. The
matrix element B is transferred in the slow (24) "slot" and will evolve
from now on with the slow frequency :
24
. The reverse is happening to
the matrix element C. The longitudinal carbon magnetization changed
sign:
( ) ( d d d d
11 22 33 44
3 2 3 2 2 )
Figure I.6b t(4) clearly shows that the second evolution t
e
/2
completes the decoupling of proton from carbon. The fast vector 13
catches up with the slow 24 and at t(4) they coincide. They have both
precessed a total angle :
H
t
e
from their starting position along y. We
can verify that the matrix elements d
*
13
and d
*
24
are equal at t(4) [see
(I.25) and (I.26)]. The transverse magnetization, calculated from the
matrix elements, is
24 Density Matrix Treatment
M M i i t i i t iM i t
TH oH H e H e oH H e
( / )[ exp( ) exp( )] exp( ) 4 2 2 : : :
After separating the real and imaginary parts in M
TH
we obtain
M iM t i t M t i t
TH oH H e H e o H e H e
(cos sin ) (sin cos ) : : : :
H
M M M t
xH TH oH H e
real part of sin :
M M M t
yH TH oH H e
coefficient of the imaginary part of cos :
This is in full accordance with the vector representation. The carbon
magnetization is still along z.
Figure I.6b t(5) shows what happened during the delay '
1
which has been chosen equal to 1/2J. Each of the two proton
magnetization components rotated by an angle :
+
'
but, with respect
to the average, the fast component has gained S /2 while the slow one
has lost S /2. As a result, the vectors are now opposite. We can verify
[see (I.30)] that at t(5) the elements d
13
and d
24
are equal and of
opposite signs. The carbon magnetization did not change.
Figure I.6c shows the situation at t(6), after the 90xH pulse.
When we went through the DM treatment, we combined the last two
pulses into a single rotation operator and this brought us directly from
D(5) to D(7). However, for the comparison with the vector repre
sentation and for an understanding of the polarization transfer, it is
necessary to discuss the density matrix D(6). It can be calculated by
applying the rotation operator R
90xH
[see (I.9)] to D(5) given in (I.33).
The result is
3 2 0 2 0
0 2 2 0 2
(6) (I.55)
2 0 3 2 0
0 2 0 2 2
s c
s c
D
c s
c s
ª º
« »
« »
« »
« »
¬ ¼
The magnetization components in Figure I.6c are derived from
the matrix elements of D(6), using (I.53). What happens to the proton
magnetization can be predicted from the previous vector representa
tion but what happens to the carbon cannot. As far as the proton is
concerned, its x components are not affected, while the other compo
nents rotate from y to z and from y to z, as expected after a 90x
pulse.
2DHETCOR 25
The net longitudinal carbon magnetization does not change, it is
still M
oC
, but a sizable imbalance is created between its fast and
slow components:
M M d d M s s
oC oC 12 11 22
2 2 3 2 ( / )( ) ( / )( 2 2 )
M s
oC
( / 1 2 2 )
(I.56)
M M d d M s s
oC oC 34 33 44
2 2 3 2 ( / )( ) ( / )( 2 2 )
M s
oC
( / 1 2 2 )
(I.57)
M M M M
zC oC
12 34
(I.58)
The imbalance term is proportional to s = sin[:
H
(t
e
+'
1
)], i.e, it is
proton modulated. When s varies from +1 to 1, the quantity 2sM
oC
varies from +2M
oC
to 2M
oC
, a swing of 4M
oC
. The remaining of the
sequence is designed to make this modulated term observable.
For s greater than 1/4, M
12
becomes positive while M
34
remains
negative. In other words, the fast carbons are now predominantly up
and the slow ones predominantly down. A correlation has been
created between the updown and the fastslow quality of the carbon
spins. The Figure I.6c is drawn for s # 0.95
The last pulse of the sequence, a 90xC, brings us to D(7) [see
(I.35)] and to Figure I.6d t(7). It is seen that the vector representation
can explain how carbon magnetization is affected by the pulse (12
goes in y and 34 in +y), but it cannot explain the nulling of proton
magnetization. Note that from t(5) on, the net magnetization was zero
(opposite vectors) but now 13 and 24 are null themselves. The density
matrix D(7) [see(I.35)] shows
M iM s
T oC 12
1 2 2 ( / )
M iM s
T oC 34
1 2 2 ( / )
Separation of the real and imaginary parts gives
M M M s
x y oC 12 12
0 1 ; ( 2 2 / )
M M M s
x y oC 34 34
0 1 ; ( 2 2 / )
The net carbon magnetization is
M M M
xC x x
12 34
0
26 Density Matrix Treatment
M M M M
yC y y oC
12 34
The proton modulated term, 2s, is not yet observable (it does not
appear in M
xC
or M
yC
). The delay '
2
will render it observable. We see
in Figure I.6d t(8) that the two components have rotated by an average
of :
C
'
2
. The fast one has gained S /2 and the slow one has lost S /2.
As a result, the two vectors (of unequal magnitude) are now
coincident. Relations (I.42) and (I.43) confirm that at time t(8) both
matrix elements d
*
12
and d
*
34
have the same phase factor, exp(i:
C
'
2
).
The net carbon magnetization is
M M d d M s s i
TC oTC oC C
( ) ( / / ) exp( )
* *
12 34 2
1 2 2 1 2 2 : '
4
2
sM i
oC C
exp( ) : '
(I.59)
The factor 4 in (I.59) represents the enhancement of the carbon
magnetization by polarization transfer. This could not be even guessed
from the vector representation.
Nothing remarkable happens after the end of '
2
. The proton
decoupler is turned on and the carbon magnetization is precessing as a
whole during the detection time t
d
(no spreadout of the fast and slow
components).
This is the end of the vector representation of the 2DHETCOR
sequence. Such representation would not have been possible without
the complete information provided by the DM treatment.
2DHETCOR 27
z
y
x
12 34
12 34
H
C
M
z13
M
z24
= =
M
o H
2
t(1)
t(2)
13
24
M
z12
M
z34
= =
M
o C
2
t(0)
:
S
H
/2
e
Jt /2
e
24
13
t
12 34
Figure I.6a. Vector representation of 2DHETCOR from t(0) to t(2).
The magnetization vectors are arbitrarily taken equal for C and H in
order to simplify the drawing. Actually the
1
H magnetization at
equilibrium is 16 times larger than that of
13
C.
28 Density Matrix Treatment
S
/2
e
Jt /
e
:
t
2
H
C
13
24
12 34
12 34
12 34
13
13
24
24
(t + ) : '
1 e H
t
e
H
:
H
H
t(3)
t(4)
t(5)
Figure I.6b. Vector representation of 2DHETCOR from t(3) to t(5).
2DHETCOR 29
34
H
C
t(6)
13
24
12
Figure I.6c. Vector representation of 2DHETCOR at time t(6). The
carbon magnetization components depend on the value of s (they are
proton modulated):
M s M
z oC 12
1 4 2 ( ) /
M s M
z oC 34
1 4 2 ( ) /
s t
H e
sin ( ) : '
1
The figure is drawn for s # 0.95.
30 Density Matrix Treatment
34
t(8)
12
34
t(7)
12
C
Figure I.6d. Vector representation of 2DHETCOR at t(7) and t(8).
The carbon magnetization components at t(7) are
M s M
y o 12
1 4 2 ( )
C
/
M s M
y34
1 4 2 ( )
oC
/ s t
H e
sin ( ) : '
1
The proton magnetization components, both fast and slow, have
vanished.
INADEQUATE 31
4. THE DENSITY MATRIX DESCRIPTION OF A
DOUBLEQUANTUM COHERENCE EXPERIMENT
(INADEQUATE)
The main goal of INADEQUATE (Incredible Natural
Abundance DoublE QUAntum Transfer Experiment) is to eliminate
the strong signal of noncoupled
13
C nuclei in order to easily observe
the 200 times weaker satellites duetoCCcoupling.Thisisrealized
by exploiting the different phase responses of the coupled and non
coupled spin signals when the phase of the observe pulse is varied
(see Figure I.7). The receiver phase is matched with the desired
signal.Itshallbeseenthatthedifferentphase behavior of the coupled
nuclei is connected withtheirdoublequantumcoherence.Thebeauty
of INADEQUATE resides in its basic simplicity: only a twostep
cycle is theoretically needed to eliminate the unwanted signal. That
the real life sequences may reach128ormorestepsisexclusivelydue
to hardware(pulse)imperfectionswhoseeffectsmustbecorrectedby
additionalphasecycling.
The essenceofINADEQUATEcanbeunderstoodbyfollowing
thebasicsequenceshowninFigureI.7.
t
d
t(0) t(1) t(8)
90
t(6) t(7)
90x
t(2) t(3)
180x
t(4) t(5)
90x 4
H
A t t
Figure I.7. The INADEQUATE sequence: 90x W 180x W
90x ' 90)
AT (proton decoupling is applied
throughouttheexperiment).
32 Density Matrix Treatment
4.1 Equilibrium Populations
At thermal equilibrium the four energy levels shown in Figure
I.8 are populated according to the Boltzmann distribution law, as
shown in (I.1) through (I.5). In this case both Q
A
and Q
X
are
13
C
transition frequencies. The difference between Q
A
and Q
X
, due to
different chemical shifts, is too small to be taken into account when
calculatingthepopulations.Weassume q = pand(I.6)becomes:
1 1
P P
2 1
(1 ) P p P
3 1
(1 ) P p P
4 1
(1 2 ) / P p P
_____________________
1 1
1 (4 4 ) p P PS
Hence,
1
1/ P S
2 3
(1 ) / P P p S
4
(1 2 ) / P p S
where 4 4 4 S p #
andthedensitymatrixatequilibriumis:
1
2
3
4
0 0 0 1 0 0 0
0 0 0 0 1 0 0
1
(0)
0 0 0 0 0 1 0 4
0 0 0 0 0 0 1 2
P
P p
D
P p
P p
ª º ª º
« » « »
« » « »
« » « »
« » « »
« »
¬ ¼ ¬ ¼
1 0 0 0 0 0 0 0
0 1 0 0 0 1 0 0
1
(I.60)
0 0 1 0 0 0 1 0 4 4
0 0 0 1 0 0 0 2
p
ª º ª º
« » « »
« » « »
« » « »
« » « »
¬ ¼ ¬ ¼
INADEQUATE 33
+1
( )
( )
0 ( )
m AX
E
1
E
2
E
3
E
4
0
( )
A
v
X
v
A
v
X
v
A
v +J/2
X
v +J/2
A
v J/2
X
v J/2
1
Figure I.8. Energy levels of a homonuclear AX system (noncoupled
andcoupled).Transition frequencies and coupling constants are in Hz.
Wewillagainignorethe(large)firsttermwhichisnotaffectedby
pulsesorevolution,putasidetheconstantfactor p/4andstartwith
0 0 0 0
0 1 0 0
(0) (I.61)
0 0 1 0
0 0 0 2
D
ª º
« »
« »
« »
« »
¬ ¼
In order to compare the results of the density matrix treatment with
those of the vectorial representation, we will calculate for every step
of the sequence the magnetization components, using the relations
(B15) (B22).Wemustalsoconsiderthathereq=pandthatM
oA
= M
oX
= M
o
/2, where M
o
refers to magnetization due to adjacent
13
C
atomsAandX.Thusourmagnetizationequationsbecome(cf.I.53):
11 22 33 44
( / 4)(
zA o
) M M d d d d
11 33 22 44
( / 4)(
zX o
) M M d d d d
* *
12 34
( / 2)(
TA o
) M M d d (I.62)
* *
13 24
( / 2)(
TX o
) M M d d
34 Density Matrix Treatment
Onecancheckthatatthermalequilibrium,whenD=D(0)
( / 4)(0 1 1 2) / 2
zA o o
M M M
( / 4)(0 1 1 2) / 2
zX o o
M M M
Thetransversemagnetization
0
TA TX
M M
4.2 The First Pulse
At time t(0) a nonselective pulse 90xAX is applied. Since all
pulses in this sequence are nonselective, the notation AX will be
omitted.Thedensitymatrix D(1) after thepulseiscalculatedaccord
ingto:
1
(0) (0) D R D
R
TherotationoperatorRanditsreciprocal
1
R
forthenonselective90x
pulsehavebeencalculatedin(I.34):
1
1 1 1 1
1 1 1 1
1 1
;
1 1 1 1 2 2
1 1 1 1
i i i i
i i i i
R R
i i i i
i i i i
ª º ª º
« » « »
« » « »
« » « »
« » « »
¬ ¼ ¬ ¼
FirstwepostmultiplyD(0)byR:
0 0 0 0
1 1
(0)
1 1
2 2 2 2
i i
D R
i i
i i
ª º
« »
« »
« »
« »
¬ ¼
INADEQUATE 35
Premultiplicationwith
1
R
leadsto
4 2 2 0 2 0
2 4 0 2 2 0
1 1
(1) (I.63)
2 0 4 2 0 2 4 2
0 2 2 4 0 2
i i i i
i i i i
D
i i i i
i i i i
ª º ª º
« » « »
« » « »
« » « »
« » « »
¬ ¼ ¬ ¼
We note that the 90
o
pulse equalizes the populations and creates sin
glequantumcoherences.Thelongitudinalmagnetizationisnullwhile
( / 2)( / 1 / 2) /
TA o o
M M i i iM 2
o
( / 2)( /1 / 2) / 2
TX o o
M M i i iM
T TA TX
M M M iM
We also note that the transverse magnetization is imaginary. Con
sideringthatM
T
=M
x
+iM
y
,itfollowsthatM
x
=0and M
y
= M
o
.
So far, thevectorrepresentationwouldhavebeenmuchsimpler
touse.Letussee,though,whathappensasweproceed.
4.3 Evolution from t (1) to t (2)
The standard formula describing the (laboratory frame) time
evolutionofthedensitymatrixelementsintheabsenceofapulseis:
( ) (0) exp( )
mn mn mn
d t d i t Z (I.64)
d
mn
is the matrix element and u
mn
= (E
m
E
n
)/ is the angular
frequency oftransitionmon.Notethatd
mn
(0)isthestartingpointof
the evolution immediately after a given pulse. In our case the ele
ments d
mn
(0) are those of D(1). If the evolution is described in a
framerotatingattransmitterfrequency u
tr
equation(I.64)becomes:
=
( ) (0) exp( ) exp[ ( ) ]
mn mn mn m n tr
d t d i t i m m t Z Z (I.65)
where m
m
andm
n
arethetotalmagneticquantumnumbers of states m
and n(seeAppendixB).
36 Density Matrix Treatment
Letusapply(I.65)toourparticularcase(m
1
=1;m
2
=m
3
=0;
m
4
= 1). As expected, the diagonal elements are invariant during
evolution since both exponentials are equal to1.Allsinglequantum
coherencesabovediagonalhavem
m
m
n
=1.Hence,
( ) (0) exp( ) exp( )
mn mn mn tr
d t d i t i t Z Z
(0) exp[ ( ) ]
mn mn tr
d i Z Z t
t : (I.66) (0) exp( )
mn mn
d i
where O
mn
istheevolutionfrequency in therotatingframe.
The rotating frame treatment is useful not only for better
visualizationofthevectorevolutionbut,also,becausethedetection is
actuallymadeattheresultinglow(audio)frequencies.
Forthedoublequantumcoherencematrixelement
14 14 14
( ) (0) exp( ) exp[ (1 1) ]
tr
d t d i t i t Z Z
(I.67)
14 14
(0) exp( ) d i t :
where O
14
= u
14
2u
tr
. We note that both single and double
quantumcoherencesevolveatlowfrequenciesintherotatingframe.
The zeroquantum coherence matrix element is not affected by
therotatingframe(m
2
m
3
=0):
(I.68)
23 23 23 23 23
( ) (0) exp( ) (0) exp( ) d t d i t d i t Z :
The zeroquantum coherence evolves at low frequency in both the
laboratoryandrotatingframe.
We now want to calculate D(2), i.e., the evoluition during the
firstdelay t.Forinstance
12 12 12 12
(2) (1) exp( ) ( / 2) exp( ) d d i i i W W : : (I.69)
Tosavespacewelet andatt(2)wehave: ( / 2) exp( )
mn mn
i i W : B
12 13
*
12 24
*
13 34
* *
24 34
1 0
1 0
(2) (I.70)
0 1
0 1
B B
B B
D
B B
B B
ª º
« »
« »
« »
« »
« »
¬ ¼
INADEQUATE 37
The zmagnetizationisstillzero(relaxationeffectsareneglected).The
transversemagnetizationcomponentsare:
* *
12 34
( / 2)(
TA o
) M M B B
12 34
( / 4)[exp( ) exp( )]
o
iM i i W W : : (I.71)
* *
13 24
( / 2)(
TX o
) M M B B
13 24
( / 4)[exp( ) exp( )]
o
iM i i W W : : (I.72)
Weseethattherearefourvectorsrotatingwith four different angular
velocities in the equatorial (xy) plane. We can identify (see Figure
I.8):
12 12 tr A
J Z Z S : :
34 A
J S : :
13 X
J S : :
24 X
J S : :
4.4 The Second Pulse
Therotationoperatorforthispulseis
1
180 180
0 0 0 1
0 0 1 0
(I.73)
0 1 0 0
1 0 0 0
yAX yAX
R R
ª º
« »
« »
« »
« »
¬ ¼
Attime t(3)thedensitymatrixis:
* *
34 24
*
1 34 13
*
24 12
13 12
1 0
1 0
(3) (2) (I.74)
0 1
0 1
B B
B B
D R D R
B B
B B
ª º
« »
« »
« »
« »
« »
¬ ¼
Two important changes have been induced by the 180
o
pulse. First,
allsinglequantumcoherenceswereconjugatedandchangedsign.
38 Density Matrix Treatment
This means that all xcomponents changed sign while the ycompo
nentsremainedunchanged:
T x y
M M iM
*
T x y
M M iM
This shows, indeed, that all four vectors rotated 180
o
around the y
axis.Second,coherencescorrespondingtofastprecessingnucleiwere
transferredin"slots"correspondingtoslowevolution.Thismeans the
vectorsalsochangedlabels.
4.5 Evolution from t (3) to t (4)
According to (I.66)and(I.74),theevolutionduringthesecondtdelay
leadsto
*
12 12 12 34 12
(4) (3) exp( ) exp( ) d d i B i W W : :
34 12
( / 2) exp( ) exp( ) i i i W W : :
12 34
( / 2) exp[ ( ) ] ( / 2) exp( 2 ) i i i i J W S W : : (I.75)
13 12
(4) ( / 2) exp( 2 ) (4) d i i J d U S W (I.76)
24 34
(4) (4) ( / 2) exp( 2 ) d d i i J V S W (I.77)
Hence,
*
*
* *
1 0
1 0
(4) (I.78)
0 1
0 1
U U
U V
D
U V
V V
ª º
« »
« »
« »
« »
« »
¬ ¼
Using(I.62)wecalculatethecorrespondingmagnetizationvectors:
0
zA zX
M M
* *
( ) cos 2
TA TX o o
M M M U V iM J S W (I.79)
We see thatwhilethechemicalshiftsrefocusedthecouplingcontinues
tobeexpressed,duetothelabelchange.
INADEQUATE 39
4.6 The Third Pulse
WeapplytoD(4)thesamerotationoperatorsweusedforthe
firstpulseandweobtain:
1 0 0
0 1 0 0
(5) (I.80)
0 0 1 0
0 0 1
c is
D
is c
ª º
« »
« »
« »
« »
¬ ¼
where c=cos2rJtands=sin2rJt.
D(5) tells us that all singlequantum coherences vanished, a
doublequantumcoherencewascreatedandtheonly existing magneti
zationisalongthezaxis.Turningtovectorrepresentation, it is seen
thatbeforethepulse[see(I.78)] wehadmagnetizationcomponentson
both x andyaxes,sinceUandVarecomplexquantities.Thevector
description wouldindicatethatthe90xpulseleavesthexcomponents
unchanged. In reality, as seen from the DM treatment, this does not
happensincealltransversecomponentsvanish.
4.7 Evolution from t (5) to t (6)
Thedoublequantumcoherenceelement, is,evolvesaccord
ingto(I.67):
*
1 0 0
0 1 0 0
(6) (I.81)
0 0 1 0
0 0 1
c w
D
w c
ª º
« »
« »
« »
« »
« »
¬ ¼
wherew= isexp( iO
14
A)= isin2rJt exp( iO
14
A).
Ourinterestisinthedoublequantumcoherencew.Inorderto
maximizeit,weselectt=(2k+1)/4Jwhere k=integer.Thenc=0
and s=sin[(2k+1)r/2]= r 1=(1)
k
40 Density Matrix Treatment
Withthisvalueoft.
1 0 0
0 1 0 0
(6) (I.82)
0 0 1 0
* 0 0 1
w
D
w
ª º
« »
« »
« »
« »
¬ ¼
where w i i
k
÷ ÷ ( ) exp( ) 1
14
O A
ThelastexpressionofD(6) tells us that atthisstagethereisno
magnetization at allinanyofthethreeaxes.Thiswouldbeimpossi
ble to derive from the vector representation, which also could not
explain the reapparition of the observable magnetization components
afterthefourthpulse.
4.8 The Fourth Pulse
This pulse is phase cycled, i.e., it is applied successively in
variouscombinationsalongthex, y, x,and yaxes.Thegeneral
expressionofthe90)AXoperatorisgiveninAppendixC[see(C39)].
2
90
2
1
* 1 1 1
(I.83)
2 * 1 1
* * * 1
AX
a a a
a a
R
a a
a a a
)
ª º
« »
« »
« »
« »
« »
¬ ¼
where a=iexp( i4)and4istheanglebetweenthexaxisandthe
directionofB
1
.When4takesthevalue0,90
o
,180
o
or270
o
,thepulse
isappliedonaxisx, y,
x,or y,respectively.
For clarity we will discuss the coupled and the noncoupled
(isolated) carbon situations separately. In the first case (coupled
13
C
spins),weobservethatat t(6)[see(I.82)]thepopulationsareequalized
andallinformationiscontainedinthewelements.
INADEQUATE 41
Theresultof is:
1
90 90
(6)
AX AX
R D R
) )
2
2 2
2 2
2
1 * *
1 *
(7) (I.84)
1 *
1
a F a G a G F
aG a F a F a G
D
aG a F a F a G
F aG aG a F
ª º
« »
« »
« »
« »
« »
¬ ¼
where (I.85)
14
( *) / 4 (1/ 2)( 1) sin
k
F w w : '
14
( *) / 4 (1/ 2)( 1) cos
k
G w w : '
D(7) shows that the newlycreatedsinglequantumcoherencescontain
thedoublequantumcoherenceinformation, O
14
.Thetransversemag
netization is zero (fast and slow vectors are equal and opposite). A
longitudinal magnetization proportional to sinO
14
appears. None of
thesecouldbededucedfromthevectorrepresentation. Yet, the den
sitymatrixwouldallowthereadertodrawthecorrespondingvectors.
To save time and space we will treat the isolated (uncoupled)
carbons as an AX system in which A and X belong to two different
molecules.Wecanuse(I.81)letting J =0(c=1;s=0;w=0):
2 0 0 0
0 1 0 0
'(6) (I.86)
0 0 1 0
0 0 0 0
D
ª º
« »
« »
« »
« »
¬ ¼
InthiscaseD(7)becomes
1 / 2 / 2 0
*/ 2 1 0 / 2
'(7) (I.87)
*/ 2 0 1 / 2
0 */ 2 */ 2 1
a a
a a
D
a a
a a
ª º
« »
« »
« »
« »
¬ ¼
D'(7) shows only single quantum coherences and equalized popula
tions. The transverse magnetization of thenoncoupled spins is equal
to their equilibrium magnetization M'
o
(its orientation depends on the
valueof4).
42 Density Matrix Treatment
4.9 Detection
Themagnetizationatt(8),duetocoupled(cpl)andnoncoupled
(ncpl) nuclei can be calculated starting from the single quantum
coherencesin(I.84)and(I.87)respectively.
12 13
( ) [exp( ) exp( )
T d d
M cpl M i t i t : :
24 34
exp( ) exp( )]
d
i t i t
d
: : (I.88)
where
0 1
* ( / 2) exp( )( 1) cos
k
o
M M aG M i ) : '
4
X d
These are the four peaks of the coupled AX system shown as a
schematiccontourplotinFigureI.9.
Forthenoncoupledcarbons
( ) '[2exp( ) 2exp( )]
T A d
M ncpl M i t i t : : (I.89)
where
' '
' */ 2 ( / 2) exp( )
o o
M M a iM i )
Thesearethetwopeaksoftheuncouplednuclei.Eachofthemis200
timesmoreintensethaneachofthefourpeaksin(I.88).
TheculminatingpointofINADEQUATEistheselectivedetec
tion of M
T
(cpl). We note that M
T
(cpl) and M
T
(ncpl) depend in
opposite ways on 4 since one contains a and the other a
*
[cf.(I.88)
and (I.89)]. They can be discriminated by cycling 4 and properly
choosing the receiver phase H [the detected signal S = M
T
exp(iH)].
The table below shows that two cycles are sufficient to eliminate
M
T
(ncpl).
Cycle
4
H
ncpl

expi(4H)
cpl

expi(4H)
1 0 0 1 1
2 90
o
90
o
1 1
(1+2) 0 2
Even small imperfections of the rf pulse will allow leakage of
the strong undesired signalintotheresultantspectrum.Thismakesit
necessarytoapplyoneofseveralcyclingpatternsconsistingofupto
INADEQUATE 43
256 steps, whichattempttocanceltheeffectsoftoolong,tooshort,or
incorrectlyphased,pulses.
4.10 CarbonCarbon Connectivity
A significant extension of INADEQUATE is its adaptation for
twodimensional experiments. The second timedomain (in addition
to t
d
) is created by making A variable. All we have to do now is to
discuss(I.88)and(I.89)intermsoftwotimevariables.
AsseeninFigureI.9,allfourpeaksofMT(cpl)willbealigned
in domain A along the same frequency O
14
= O
A
+ O
X
. The great
advantage of the 2D display consists of the fact that every pair of
coupled carbons will exhibit its pair of doublets along its own O
14
frequency. This allows us to trace out the carbon skeleton of an
organicmolecule.
O
A
O
d
O
A
O
14
O
X
÷O
14
0
Figure I.9. The four peaksduetoapairofcoupled
13
Catoms.The
verticalscaleistwicelargerthanthehorizontalscale.
44 Density Matrix Treatment
Thestudentisinvitedtoidentifythemoleculewhose2D
spectrumisshowninFigureI.10andtodetermineitscarbon
carbonconnectivities.Theanswerisinthefootnoteonpage59.
It should be noted that M
T
(ncpl) does not depend on A
[cf.(I.81)].Thismeansthat,whenincompletelyeliminated,thepeaks
of isolated carbons will be "axial" (dotted circles on the zero
frequencylineofdomain ').
WealsonotethatM
T
(cpl)isphasemodulatedwithrespecttot
d
and amplitude modulated with respect to '. Consequently, mirror
image peaks will appear at frequencies :
14
. This reduces the
intensity of the displayed signals and imposes restrictions on the
choice of the transmitter frequency, increasing the size of the data
matrix. A modified sequence has been proposed to obtain phase
modulation with respect to ', the analog of a quadrature detection in
domain '.
~
~
~
~
53.1 34.2 26.0 12.1ppm
Figure I.10. The carboncarbonconnectivityspectrumofamolecule
withMW=137.
COSY 45
5. DENSITY MATRIX DESCRIPTION OF COSY
(HOMONUCLEAR CORRELATION SPECTROSCOPY)
COSY(COrrelation SpectroscopY)iswidelyused,particularly
fordisentanglingcomplicatedprotonspectraby protonproton chemi
cal shift correlation and elucidation of the coupling pattern. Of
course, other spin 1/2 systems such as
19
F can be successfully studied
withthis2Dsequence.ThebasicsequenceisshowninFigureI.11.
t
d
t(0) t(1) t(4)
90x
t(2) t(3)
90x
t
e
Figure I.11. The Basic COSY sequence (without phase cycling):
90x t
e
90x AT ÷ ÷ ÷
5.1 Equilibrium Populations
Since we deal with a homonuclear AX system, the populations
at thermal equilibrium follow a pattern identical to that of INADE
QUATE(seeI.60andI.61).Theinitialdensitymatrixis:
0 0 0 0
0 1 0 0
(0)
0 0 1 0
0 0 0 2
D
(
(
(
=
(
(
¸ ¸
(I.90)
46 Density Matrix Treatment
5.2 The First Pulse
Here, also, we can use the results from INADEQUATE (I.63)
sincethefirstpulseisanonselective90xAX:
2 0
2 0
1
(1) (I.91)
0 2 2
0 2
i i
i i
D
i i
i i
÷ ÷ (
(
÷
(
=
( ÷
(
¸ ¸
5.3 Evolution from t (1) to t (2)
Only nondiagonaltermsareaffectedbyevolution.Thesingle
quantumcoherenceswillevolve,each withitsownangularfrequency,
leadingto:
1 0
* 1 0
(2) (I.92)
* 0 1
0 * * 1
A B
A C
D
B D
C D
(
(
(
=
(
(
¸ ¸
where
( ) ( )
( ) (
( ) (
( ) (
12
13
24
34
/ 2 exp
/ 2 exp
/ 2 exp
/ 2 exp
e
e
e
e
A i i t
)
)
)
B i i
C i i t
D i i t
= ÷ ÷ O
= ÷ ÷ O
= ÷ ÷ O
= ÷ ÷ O
t
R
(I.93)
5.4 The Second Pulse
To calculate , we use the rotation operators
forthe90xAXpulsegivenin(I.34)
1
(3) (2) D R D
÷
=
1
1 1 1 1
1 1 1 1
1 1
;
1 1 1 1 2 2
1 1 1 1
i i i i
i i i i
R R
i i i i
i i i i
÷
÷ ÷ ÷ ÷ ( (
( (
÷ ÷
( (
= =
( ( ÷ ÷
( (
÷ ÷
¸ ¸ ¸ ¸
÷ ÷
÷ ÷
÷ ÷
COSY 47
Thepostmultiplication D(2)Ryields
1 1
* 1 * 1 * *
1
* 1 * 1 * * 2
1 * * * * * * 1 * *
iA iB i A B i A B iA iB
i A C iA iC iA iC i A C
i B D iB iD iB iD i B D
iC iD i C D i C D iC iD
+ + + ÷ ÷ + ÷ + + (
(
+ ÷ + + ÷ + + ÷ +
(
( + ÷ ÷ + + + + ÷ +
(
÷ + + + ÷ ÷ + + +
¸ ¸
Wethenpremultiplythisresultby
1
R
÷
andobtain
1
(3) (2) D R D R
÷
=
4 * * *
* * *
* * *
* * *
* 4 * * *
* * *
* * *
* * *
1
4
iA iA A A A A iA iA
iB iB B B B B iB iB
iC iC C C C C iC iC
iD iD D D D D iD iD
A A iA iA iA iA A A
B B iB iB iB iB B B
C C iC iC iC iC C C
D D iD iD iD iD D D
A
+ ÷ + + ÷ + + +
+ ÷ ÷ + + + + +
+ ÷ + ÷ + + ÷ ÷
+ ÷ + + + ÷ ÷ ÷
+ + ÷ + + + + ÷
+ ÷ + ÷ ÷ ÷ + +
÷ + + ÷ + + + +
+ + ÷ + ÷ ÷ ÷ +
=
+ ÷ * * 4 *
* * *
* * *
* * *
* * * 4
* * * *
* * *
* * *
A iA iA iA iA A A
B B iB iB iB iB B B
C C iC iC iC iC C C
D D iD iD iD iD D D
iA iA A A A A iA iA
iB iB B B B B iB iB
iC iC C C C C iC iC
iD iD D D D D iD iD
÷ ÷ + ÷ + +
+ + + + ÷ + + ÷
+ + ÷ ÷ ÷ + ÷ +
÷ + + + + ÷ + +
÷ ÷ ÷ + + + ÷ +
÷ ÷ + + ÷ + ÷ +
+ + + + + ÷ ÷ +
+ + + ÷ + + ÷ +
¸
( *
*
*
*
*
*
*
*
*
*
*
*
*
*
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
¸
(I.94)
48 Density Matrix Treatment
Onecancheckthatthepopulationsum
11 22 33 44
d d d d + + + (traceof
thematrix)isinvariant,i.e.,ithasthesamevalueforD(0)through
D(3).Also,D(3)isHermitian(thedensitymatrixalwaysis).Indoing
thisverificationwekeepinmindthatthesums * A A + , * B B + ,
etc.,areallrealquantities,whilethedifferences * A A ÷ , * B B ÷ ,
etc.,areimaginary. Thiscanbeusedtosimplifytheexpressionof
D(3)byemployingthefollowingnotations:
( ) ( )
12 12 12
( / 2) exp ( / 2) cos sin
e e
A i i t i t i t = ÷ ÷ O = ÷ O ÷ O =
e
) ic
12 12 12 12
( / 2)( ) (1/ 2)( ) i c is s ic = ÷ ÷ = ÷ +
12 12
* (1/ 2)( A s = ÷ ÷
WithsimilarnotationsforB, C,andDweobtain:
( )( )
12 12 12 12
1 2 ; * ; * A s ic A A s A A = ÷ + + = ÷ ÷ = ÷ic
( )( )
13 13 13 13
1 2 ; * ; * B s ic B B s B B ic = ÷ + + = ÷ ÷ = ÷
( )( )
24 24 24 24
1 2 ; * ; * C s ic C C s C C = ÷ + + = ÷ ÷ = ÷ic (I.95)
( )( )
34 34 34 34
1 2 ; * ; * D s ic D D s D D = ÷ + + = ÷ ÷ = ÷ic
Withthenewsine/cosinenotations,D(3)becomes:
12 13 12 13 12 13 12 13
24 34 24 34 24 34 24 34
12 13 12 13 12 13 12 13
24 34 24 34 24 34 24 34
12 13 12 13 12 13
24 34 24 34 24 3
4
4
1
4 4
c c s ic ic s is is
c c ic s s ic is is
s ic c c is is ic s
ic s c c is is s ic
ic s is is c c
s ic is is c c
+ + ÷ + ÷ ÷ ÷
+ + ÷ ÷ ÷ ÷ + +
÷ ÷ ÷ + ÷ + ÷ ÷
+ ÷ + ÷ ÷ + ÷ +
÷ ÷ ÷ + ÷
÷ + + ÷ ÷ +
12 13
4 24 34
12 13 12 13 12 13 12 13
24 34 24 34 24 34 24 34
(I.96)
4
s ic
ic s
is is ic s s ic c c
is is s ic ic s c c
÷ ÷
+ ÷
+ ÷ ÷ + ÷ ÷
÷ ÷ ÷ ÷ ÷ ÷ ÷ ÷
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
¸ ¸
COSY 49
5.5 Detection
Sincenootherpulsefollowsaftert(3)wewillconsideronly the
evolution of the observable (single quantum) elements d
12
, d
34
, d
13
,
and d
24
inthetimedomain t
d
.Beforeevolutiontheyare(fromI.96):
( )( )
12 12 34 13 24
(3) 4 d i is is c c = + + + ÷
( )( )
34 12 34 13 24
(3) 4 d i is is c c = + + ÷ +
( )( )
13 12 34 13 24
(3) 4 d i c c is is = + ÷ + + (I.97)
( )( )
24 12 34 13 24
(3) 4 d i c c is is = ÷ + + +
Their complex conjugates, which are needed for the calculation of
magnetizationcomponents,are:
( )( )
*
12 12 34 13 24
(3) 4 d i is is c c = + + ÷ +
( )( )
*
34 12 34 13 24
(3) 4 d i is is c c = + + + ÷
( )( )
*
13 12 34 13 24
(3) 4 d i c c is is = ÷ + + + (I.98)
( )( )
*
24 12 34 13 24
(3) 4 d i c c is is = + ÷ + +
Each of the four matrix elements above contains all four frequencies
evolving in domain t
e
, namely:
12 34 13 24
, , , and .
e e e
t t t
e
t O O O O
Duringdetection,eachofthem will evolvewithitsownfrequencyin
thedomain t
d
:
( )( ) ( )
*
12 12 34 13 24 12
(4) 4 exp
d
d i is is c c i = + + ÷ + O t
( )( ) ( )
*
34 12 34 13 24 34
(4) 4 exp
d
d i is is c c i = + + + ÷ O t
( )( ) ( )
*
13 12 34 13 24 13
(4) 4 exp
d
d i c c is is i = ÷ + + + O t (I.99)
( )( ) ( )
*
24 12 34 13 24 24
(4) 4 exp
d
d i c c is is i t = + ÷ + + O
Expression(I.99)showsthateacht
d
frequencyismodulatedby
allfourt
e
frequencies.Thus,weexpectsixteenpeaksinthe2Dplot.
Actually, there will be 32 peaks, because only thet
d
domain is phase
modulated, while the t
e
domain is amplitude modulated (i.e., it
containssine/cosineexpressions).
50 Density Matrix Treatment
Each sine or cosine implies both the positive and the negative
frequencyaccordingto
( ) (
1
cos exp exp
2
jk jk e jk e jk e
c t i t i t
)
(
= O = O + ÷ O
¸ ¸
( ) (
1
sin exp exp
2
jk jk e jk e jk e
is i t i t i t
)
(
= O = O ÷ ÷ O
¸ ¸
Thisleadstothe32peakcontourplotinFigureI.12.
13
24
24
13
13
24
12
12
12
34
34
34
:
:
e
d
Figure I.12. Contour plot of COSY without phase cycling. The
transmitterfrequencyisononesideofthespectrum.
COSY 51
We can plot the positivefrequenciesonly,buttheamplitude
modulationindomain t
e
stillisamajordrawbacksinceitrequires
placing the transmitter frequency outside the spectrum (i.e., we
lose the advantage of quadrature detection in both domains). The
spectralwidthshavetobedoubledand thedatamatrixincreasesby
afactoroffour.
If the transmitter is placed within the spectrum (e.g., between
:
12
and:
24
),amessypatternisobtainedasshown in Figure I.13. The
next section shows how this can be circumvented by means of an
appropriatephasecycling.
:
d
13
24
12
34
:
e
13
24
12
34
24 13 12 34
Figure I.13. Contour plot of COSY without phase cycling. If the
transmitterisplacedwithinthespectrum,itcausesoverlapofpositive
andnegativefrequencies.
52 Density Matrix Treatment
6. COSY WITH PHASE CYCLING
6.1 Comparison with the Previous Sequence
The sequence for COSY with phase cycling shown in Figure
I.14 differs from that discussed above (Figure I.11) only by the
cyclingofthesecondpulse.
t
d
t(0) t(1) t(4)
90
t(2) t(3)
90x
t
e
)
Figure I.14. COSY sequence with phase cycling of second pulse:
90x t
e
90) AT ÷ ÷ ÷
Moreover, only two steps are theoretically necessary to
eliminate negative frequencies in domain t
e
. The second pulse is
successivelyphasedin xandy.Ratherthandoingthedensitymatrix
calculations for an arbitrary phase ), we will take advantage of the
fact that we have already treated the x phase in the previous section.
Onlytheeffectof90yAXmustthenbecalculated(seeFigureI.15).
Since the two sequences in Figures I.11 and I.15 have a
common segment [t(0) to t(2)], we can take D(2) from the previous
section[see(I.92).and(I.93)].
1 0
* 1 0
(2)
* 0 1
0 * * 1
A B
A C
D
B D
C D
(
(
(
=
(
(
¸ ¸
(I.100)
COSY 53
t
d
t(0) t(1) t(4)
90y
t(2) t(3)
90x
t
e
Figure I.15. The second step of the phase cycled COSY sequence:
90x t
e
90y AT ÷ ÷ ÷
6.2 The Second Pulse
The rotation operator for the 90yAX pulse can be obtained by
multiplyingR
90yA
byR
90yX
.Theseoperatorsare(seeAppendixC):
90 90
1 1 0 0 1 0 1 0
1 1 0 0 0 1 0 1
1 1
;
0 0 1 1 1 0 1 0
2 2
0 0 1 1 0 1 0 1
yA yX
R R
( (
( (
÷
( (
= =
( ( ÷
( (
÷ ÷
¸ ¸ ¸ ¸
Theresultofthemultiplication,
90 yAX
R R = , isshownbelowtogether
withitsreciprocal,
1
R
÷
.
1
1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1
1 1
;
1 1 1 1 1 1 1 1 2 2
1 1 1 1 1 1 1 1
R R
÷
÷ ÷ ( (
( (
÷ ÷ ÷ ÷
( (
= =
( ( ÷ ÷ ÷ ÷
( (
÷ ÷
¸ ¸ ¸ ¸
(I.101)
54 Density Matrix Treatment
Thepostmultiplication D(2)Ryields
1 1 1 1
1 * 1 * 1 * 1 *
1
1 * 1 * 1 * * 2
1 * * 1 * * 1 * * 1 * *
A B A B A B A B
A C A C A C A C
B D B D B D i B D
C D C D C D C D
÷ ÷ + ÷ ÷ + + + (
(
÷ + + + ÷ ÷ + ÷ + +
(
( ÷ + + ÷ + ÷ + ÷ + +
(
÷ ÷ ÷ + ÷ ÷ ÷ + + +
¸ ¸
Premultiplyingthisresultby
1
R
÷
gives
1
(3) (2) D R D R
÷
= =
4 * * *
* * *
* * *
* * *
* 4 * * *
* * *
* * *
* * *
1
* * 4
* *
* *
*
A A A A A A A A
B B B B B B B B
C C C C C C C C
D D D D D D D D
A A A A A A A A
B B B B B B B B
C C C C C C C C
D D D D D D D D
A A A A
B B B B
C C C C
D D D
÷ ÷ + ÷ ÷ ÷ + ÷
÷ ÷ ÷ ÷ + ÷ + ÷
÷ ÷ + + + ÷ ÷ +
÷ ÷ + ÷ + + ÷ +
÷ + + + ÷ + +
÷ ÷ ÷ ÷ + ÷ + ÷
+ + ÷ ÷ ÷ + + ÷
÷ + + + + ÷ ÷ ÷
÷ ÷ + ÷
÷ + ÷ +
÷ + + ÷
+ + ÷
4 *
* *
* *
* *
* * * 4
* * *
* * *
* * *
A A A A
B B B B
C C C C
D D D D D
A A A A A A A A
B B B B B B B B
C C C C C C C C
D D D D D D D D
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
÷ ÷ + ÷
(
(
+ + + +
(
+ + ÷ ÷
(
(
+ ÷ ÷ + ÷
(
(
(
(
÷ + + + ÷ + + +
(
÷ + ÷ + + + + +
(
(
+ ÷ ÷ + ÷ ÷ + +
(
+ ÷ ÷ ÷ ÷ + + +
(
(
¸ ¸
(
*
*
*
*
*
*
*
*
*
*
*
*
*
(I.102)
COSY 55
Withthesamenotationsasin(I.95):
( )( )
12 12 12 12
1 2 ; * ; * A s ic A A s A A = ÷ + + = ÷ ÷ = ÷ic
( )( )
13 13 13 13
1 2 ; * ; * B s ic B B s B B ic = ÷ + + = ÷ ÷ = ÷
( )( )
24 24 24 24
1 2 ; * ; * C s ic C C s C C = ÷ + + = ÷ ÷ = ÷ic (I.103)
( )( )
34 34 34 34
1 2 ; * ; * D s ic D D s D D = ÷ + + = ÷ ÷ = ÷ic
D(3)becomes
12 13 12 13 12 13 12 13
24 34 24 34 24 34 24 34
12 13 12 13 12 13 12 13
24 34 24 34 24 34 24 34
12 13 12 13 12 13
24 34 24 34 24
4
4
1
4 4
s s ic s s ic ic ic
s s s ic ic s ic ic
ic s s s ic ic s ic
s ic s s ic ic ic s
s ic ic ic s s
ic s ic ic s
+ + ÷ + + ÷ ÷ ÷
+ + ÷ ÷ ÷ ÷ + +
+ + ÷ + + ÷ ÷ ÷
÷ + + ÷ + ÷ ÷ +
+ + ÷ + + ÷
+ ÷ ÷ + ÷ +
12 13
34 24 34
12 13 12 13 12 13 12 13
24 34 24 34 24 34 24 34
(I.104)
4
ic s
s s ic
ic ic s ic ic s s s
ic ic ic s s ic s s
÷ ÷
+ ÷
+ + ÷ + + ÷ ÷ ÷
÷ ÷ + + + + ÷ ÷
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
¸ ¸
Wehavetoconsideronlytheobservablematrixelements:
( )( )
( )( )
( )( )
( )(
12 12 34 13 24
34 12 34 13 24
13 12 34 13 24
24 12 34 13 24
(3) 4
(3) 4
(3) 4
(3) 4
d i c c is is
d i c c is is
d i is is c c
d i is is c c
= ÷ ÷ ÷ +
= ÷ ÷ + ÷
= ÷ + ÷ ÷
= + ÷ ÷ ÷ )
(I.105)
56 Density Matrix Treatment
Comparingtheresultsforphasey(I.105)withthoseforphasex
(I.97)showsthatcand ÷ isareinterchangedinallterms.Thiswill
leadtothedesiredphasemodulation.Additionof(I.97)and(I.105)
gives
( ) ( )
12 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i is c is c c is c is = ÷ + ÷ + ÷ + ÷ + (
¸ ¸
( ) ( )
34 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i is c is c c is c is = ÷ + ÷ + ÷ + + ÷ (
¸ ¸
( ) ( )
13 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i c is c is is c is c = ÷ + ÷ + + ÷ + ÷ (
¸ ¸
( ) ( )
24 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i c is c is is c is c = ÷ + + ÷ + ÷ + ÷ (
¸ ¸
(I.106)
Thecomplexconjugatesofthematrixelementsabove(neededforthe
expressionofthemagnetizationcomponents)are
( ) ( )
*
12 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i is c is c c is c is = + + + + ÷ ÷ + + (
¸ ¸
( ) ( )
*
34 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i is c is c c is c is = + + + + + + ÷ ÷ (
¸ ¸
( ) ( )
*
13 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i c is c is is c is c = ÷ ÷ + + + + + + (
¸ ¸
( ) ( )
*
24 12 12 34 34 13 13 24 24
(3) 4 ) ( ) ( ) ( d i c is c is is c is c = + + ÷ ÷ + + + + (
¸ ¸
(I.107)
Weobservethateveryparenthesisrepresentsanexponential,therefore
wecanusethenotation
( )
exp
jk jk jk jk e
e c is i t = + = O (I.108)
Withthisnotation(I.107)becomes
( )( )
*
12 12 34 13 24
(3) 4 d i e e e e = + + ÷ +
( )( )
*
34 12 34 13 24
(3) 4 d i e e e e = + + + ÷
( )( )
*
13 12 34 13 24
(3) 4 d i e e e e = ÷ + + + (I.109)
( )( )
*
24 12 34 13 24
(3) 4 d i e e e e = + ÷ + +
COSY 57
Thereaderisremindedthattheaboveexpressionsrepresentthe
summationfromtwoacquisitions,onewithphasexandtheotherwith
phase yforthesecondpulse.Insteadofsinesorcosines,theycontain
onlyexponentials.Inotherwordswehaveachievedphasemodula
tioninthedomain t
e
.
6.3 Detection
The evolution during t
d
is identical for the two acquisitions,
thereforewecanapplyitafterthesummation(inI.109).
( )( ) ( )
*
12 12 34 13 24 12
(4) 4 exp
d
d i e e e e i = + + ÷ + O t
( )( ) ( )
*
34 12 34 13 24 34
(4) 4 exp
d
d i e e e e i = + + + ÷ O t
( )( ) ( )
*
13 12 34 13 24 13
(4) 4 exp
d
d i e e e e i = ÷ + + + O t (I.110)
( )( ) ( )
*
24 12 34 13 24 24
(4) 4 exp
d
d i e e e e i t = + ÷ + + O
The expressions (I.110) correspond to a contour plot with 16
peaks,asrepresentedinFigure I.16.Thispatternisnolongerdepend
ent on the position of the transmitter since we have achieved the
equivalent of quadrature detection in both domains. There are four
diagonal terms, each having the same frequency in both domains t
e
and t
d
. If the two frequencies differ only by J (e.g., we have :
12
in
domain t
e
and:
34
indomain t
d
)wehavea"neardiagonal"peak.There
are four such peaks. The remaining eight are referred to as off
diagonalorcrosspeaksandtheirpresenceindicatesthat spins A and
X are coupled. Two noncoupled spins will exhibit only diagonal
peaks. We can verify that this is so by discussing what happens if J
becomesvanishinglysmall.Inthis case :
12
=:
34
=:
A
(centerofthe
doublet);likewise:
13
=:
24
=:
X
.Thereforeeachgroupof4peaksin
Figure I.16 collapses into a single peak in the center of the
corresponding square. The diagonal and neardiagonal peaks of
nucleus A are all positive and they collapse into one diagonal peak,
four times larger. The same is true for nucleus X. The offdiagonal
peaks come in groups of four, two positive and two negative. When
they collapse (J=0) they cancel each other and there will be no off
diagonal peak.Thenetresultisaspectrumwithjusttwopeaks,both
onthediagonal,withfrequencies :
A
and :
X
.Theabovediscussion
58 Density Matrix Treatment
showsthatCOSYisnotsuitedforspectrawithillresolvedmultiplets
becausetherewillbedestructiveoverlapintheoffdiagonalgroups.
13
24
24 13 12
12
34
34
:
:
e
d
Figure I.16. ContourplotofCOSYwithphasecycling.Opencircles
arepositivepeaks;shadedcirclesarenegativepeaks.
There is one more observation. It is common practice to plot
the 2D spectra in the "magnitude calculation" (MC) or "absolute
value" mode, to avoid phasing problems. The magnitude calculation
(the absolute value of a complex quantity) is performed by the
computer after Fourier transform in both domains. Two peaks, one
positive and onenegative,willbothbecomepositiveinMC,provided
they are well resolved. If they are illresolved, they will cancel each
other partially and will yield a much smaller signal. The MC is
appliedtothissignalanditcannotrepresenttheoriginalamplitudeof
the two peaks. Therefore the use of magnitude calculation does not
provideasolutionforpoorlyresolvedmultiplets.
One word about the utility of phase cycling. While it is well
known that this procedure helps canceling out radiofrequency
interferencesandpulseimperfections,wehavejustseenthatitcanbe
COSY 59
useful for other purposes. In INADEQUATE it helps eliminate the
NMRsignalfromthe
13
C
12
Cpairswhilepreservingthatfrom
13
C
13
C
pairs. In COSY it helps achieve phase modulation in domain t
e
. In
both cases a two step cycling is theoretically sufficient.However,to
efficiently compensate for hardware imperfections, cycling in more
thantwostepsisgenerallyemployed.
7. CONCLUSION OF PART I
Thedensitymatrixapproachdescribedaboveconstitutesavery
clearandusefulmeansforunderstandingthemultipulsesequencesof
modern NMR. The limitation of this approach is the rapidly
increasing volume of calculation with increasing number of nuclei.
Thesizeofthematrixgoesfrom16elementsforatwospin1/2system
to64and256elementsforthreeandfourspinsystems,respectively.
We must therefore resort to an avenue which affords a
"shorthand" for the description of rotations and evolutions. The new
avenuewepresentinthesecondpartofthismonographistheproduct
operatorformalism.
________________________________________________________
Answer to the problem on page 44: The contour plot in Figure I.10 is the
carboncarbonconnectivityspectrumof2bromobutane.
60
2
The Product Operator Formalism
1. INTRODUCTION
Inthissectionwewillseethatthedensitymatrixatequilibrium
canbeexpressedintermsofthespinangularmomentumcomponentI
z
of each nucleus. Moreover, effects of pulses (rotations) and evolu
tions of noncoupled spins can also be described in terms of angular
momentumcomponents(I
x
,I
y
,I
z
).However,inordertoexpressevolu
tions of coupled spins, we will need additional "building blocks"
besides angular momentum components. We will thus introduce a
"basis set" which is composed of "product operators." The latter are
either products between angular momentum components or products
of angular momentum components with the unit matrix. We will
describe this approach and will apply it to several pulse sequences,
beginningwith2DHETCOR.
2. EXPRESSING THE DENSITY MATRIX IN TERMS
OF ANGULAR MOMENTUM COMPONENTS
We start with the same procedure of describing the density
matrix at equilibrium, D(0), as in Part I. In order to generalize the
approach to an AX (not only a CH) system we preserve separate
Boltzmanfactors,1+p and1+q,fornucleiAandX,respectively
[see(I.35)]:
The PO Formalism 61
1 0 0 0
0 1 0 0
1
(0) (II.1)
0 0 1 0
0 0 0 1
p
D
q N
p q
(
(
+
(
=
( +
(
+ +
¸ ¸
Nisthenumberofstates(4foranAXsystem).
As we did in Part I, weseparatetheunitmatrixfromthematrix
representing population differences. However, here we choose as a
factorfortheunitmatrixtheaveragepopulation(1+p/2+q/2)/N:
1 / 2 / 2
(0)
p q
D
N
+
(
(
+
(
=
(
(
(
¸ ¸
1 0 0 0
0 1 0 0
0 0 1 0
0 0 0 1
/ 2 / 2 0 0 0
0 / 2 / 2 0 0
1
0 0 / 2 / 2 0
0 0 0 / 2
p q
p q
p q N
p q
÷ ÷ (
(
÷
(
+
( ÷ +
(
+
¸ ¸
/ 2
(II.2)
Again, we ignore the term containing the unit matrix which does not
contributetomagnetization.
/ 2 / 2 0 0 0
0 / 2 / 2 0 0
1
(0)
0 0 / 2 / 2 0
0 0 0 / 2
p q
p q
D
p q N
p q
÷ ÷ (
(
÷
(
=
( ÷ +
(
+
¸ ¸
/ 2
(II.3)
62 Product Operator Treatment
Separationofthepandqtermsgives
1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 0
(0) (II.4)
0 0 1 0 0 0 1 0 2 2
0 0 0 1 0 0 0 1
p q
D
N N
( (
( (
÷
( (
= ÷ ÷
( ( ÷
( (
÷ ÷
¸ ¸ ¸ ¸
We recognize in the first term the angular momentum component I
zA
and, in the second term, I
zX
[see (C13) and (C15)]. We note that the
signs of the magnetic quantum numbers are in the same order as in
FigureI.1ofPartI.WecannowwriteD(0)inshorthand:
(0)
zA zX
p q
D I
N N
= ÷ ÷ I (II.5)
3. DESCRIBING THE EFFECT OF A PULSE
IN TERMS OF ANGULAR MOMENTA
Therotationoperatorfora90
o
pulsealongthexaxisonnucleus
Xis:
90
1 0 0
0 1 0
1
(seeI.9)
0 1 0
2
0 0 1
xX
i
i
R
i
i
(
(
(
=
(
(
¸ ¸
Itsreciprocalis:
1
90
1 0 0
0 1 0
1
(seeI.10)
0 1 0
2
0 0 1
xX
i
i
R
i
i
÷
÷ (
(
÷
(
=
( ÷
(
÷
¸ ¸
The PO Formalism 63
Wepostmultiply D(0)from(II.3)withR
90xX
(R,forbrevity).
0 0 0 1 0
0 0 0 0 1
1 1
(0)
0 0 0 0 1 2 2
0 0 0 0 0
p q i 0
0
0
1
p q i
D R
p q i N
p q i
÷ ÷ (
(
÷
(
=
( ÷ +
(
+
¸ ¸
(
(
(
(
(
¸ ¸
0 0
0 0
1
(II.6)
0 0
2 2
0 0
p q ip iq
p q ip iq
ip iq p q
N
ip iq p q
÷ ÷ ÷ ÷ (
(
÷ ÷
(
=
( ÷ + ÷ +
(
+ +
¸ ¸
Wenowpremultiplythisresultby R
1
D(1)=R
1
[D(0) R]
1
4
1 0 0 0 0
0 1 0 0 0
0 1 0 0 0
0 0 1 0 0
N
i p q ip iq
i p q ip
i ip iq p q
i ip iq
÷ ÷ ÷ ÷ ÷ (
(
÷ ÷
(
=
( ÷ ÷ + ÷ +
(
÷ +
¸ ¸ ¸
iq
p q
(
(
÷
(
(
(
+
¸
(II.7)
2 0 2 0 0 0
0 2 0 2 0 0
1 1
2 0 2 0 0 0 4 2
0 2 0 2 0 0
p iq p iq
p iq p iq
iq p iq p N N
iq p iq p
÷ ÷ ÷ ÷ (
(
÷ ÷
(
= =
( ÷ ÷
(
¸ ¸ ¸
(
(
(
(
(
¸
Separationofpandqyields
1 0 0 0 0 0 0
0 1 0 0 0 0 0
(1) (II.8)
0 0 1 0 0 0 0 2 2
0 0 0 1 0 0 0
i
i
p q
D
i N N
i
÷ ( (
( (
÷ ÷
÷
( (
= +
( (
( (
÷
¸ ¸ ¸ ¸
64 Product Operator Treatment
Comparing the result with (C13) and (C14) we recognize I
zA
and I
yX
andwecanwrite
(1)
zA yX
p q
D I
N N
I
÷
= + (II.9)
Relations (II.5) and (II.9) open the way toward the product
operatorformalism.WesucceededinwritingD(0)andD(1)inangu
lar momentumshorthand.Moreover,weforeseethepossibilityofob
taining the result of pulses without matrix calculations; this can be
seenbysimplyrepresentingtheangularmomentaintheir vector form,
asinFigureII.1.
90xX
z
y
x
z
y
x
(q/N)I
zX
(p/N)I
zA
(p/N)I
zA
(q/N)I
yX
( / ) ( / )
zA zX
p N I q N I ÷ ÷
90xX
÷÷÷÷ ( / ) ( / )
zA yX
p N I q N I ÷ +
Figure II.1.Effectofthe90xXpulse.
We note that, because of our convention to take gamma as negative
(seeAppendixJ)theangularmomentumvectororientationisopposite
tothatofthemagnetizationvectorwhichwasusedinPartI.
The PO Formalism 65
4. AN UNSUCCESSFUL ATTEMPT TO DESCRIBE A
COUPLED EVOLUTION IN TERMS OF ANGULAR
MOMENTA
Letuscalculatetheresultofacoupledevolutionofdurationt
e
/2
startingfrom D(1).Applying(I.13)toD(1)in(II.7)gives:
0 0
0 0
1
(2) (II.10)
* 0 0 2
0 * 0
p F
p G
D
F p N
G p
÷ (
(
(
=
( ÷
(
¸ ¸
where
13
exp( / 2)
e
F iq i t = ÷ ÷ O
24
exp( / 2)
e
G iq i t = ÷ ÷ O (II.11)
Withthenotations
13 X
J t O = O +
24 X
J t O = O ÷ (II.12)
theexponentialsin(II.11)become
13
exp( / 2) exp[ ( ) / 2]
e X
i t i J t
e
t ÷ O = ÷ O +
exp( / 2) exp( / 2)
X e e
i t i Jt t = ÷ O ÷ (II.13)
24
exp( / 2) exp[ ( ) / 2]
e X
i t i J t
e
t ÷ O = ÷ O ÷
exp( / 2) exp( / 2)
X e e
i t i Jt t = ÷ O +
Wemakenowthefollowingnotations:
cos / 2 sin / 2
X e X e
c t s t = O = O
cos / 2 sin / 2
e
C Jt S Jt
e
t t = = (II.14)
Notethatherecandshavedifferentmeaningsthanthe ones assigned
inPartI(I.31).Tomakesure,cands(lowercase)representeffectsof
chemical shift and C and S (upper case) represent effects of J
coupling.Nowtheexponentialsin(II.11)canbewrittenas:
13
exp( / 2) ( )( )
e
i t c is C iS ÷ O = ÷ ÷ (II.15)
24
exp( / 2) ( )( )
e
i t c is C iS ÷ O = ÷ +
66 Product Operator Treatment
Then FandGbecome
( )( ) ( ) ( F iq c is C iS iq cC sS q sC cS = ÷ ÷ ÷ = ÷ ÷ ÷ + )
) (II.16) ( )( ) ( ) ( G iq c is C iS iq cC sS q sC cS = ÷ ÷ + = ÷ + ÷ ÷
andwecanrewriteD(2)as
( )
0 0
( )
( )
0 0
( )
1
( ) 2
0 0
( )
( )
0 0
( )
iq cC sS
p
q sC cS
iq cC sS
p
q sC cS
iq cC sS N
p
q sC cS
iq cC sS
p
q sC cS
÷ ÷ (
÷
(
÷ +
(
( ÷ +
(
÷ ÷
(
(
÷
÷ (
÷ +
(
(
+
(
÷ ÷ (
¸ ¸
(II.17)
WeseparateD(2)intofivematricescontainingthefactorsp, qcC, qsS,
qsC,andqcS:
1 0 0 0 0 0 0
0 1 0 0 0 0 0
(2)
0 0 1 0 0 0 0 2 2
0 0 0 1 0 0 0
i
i
p q
D cC
i N N
i
÷ (
(
÷ ÷
(
= ÷ +
(
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
0 0 0 0 0 1 0
0 0 0 0 0 0 1
0 0 0 1 0 0 0 2 2
0 0 0 0 1 0
i
i
q q
sS sC
i N N
i
÷ (
(
(
÷ ÷
(
(
÷
¸ ¸ ¸
0
(
(
(
(
(
¸
0 0 1 0
0 0 0 1
(II.18)
1 0 0 0 2
0 1 0 0
q
cS
N
(
(
÷
(
÷
(
(
÷
¸ ¸
The PO Formalism 67
In(II.18)onlythreeterms,thefirst,second,andfourth,contain
angularmomenta[cf.(C12C15)].Thefirsttermis ÷ (p/N)I
zA
,the
secondis(q/N)cCI
yX
andthefourthis ÷ (q/N)sCI
xX
.Thethirdand
fifthmatricesin(II.18)containneitherangularmomentanoralinear
combinationofthesixcomponents(I
xA
, I
yA
, I
zA
, I
xX
, I
yX
, I
zX
)knownto
us.Thisshowsthatthesixangularmomentumcomponentsshownin
parenthesisarenotsufficienttoexpressthedensitymatrixaftera
coupledevolution.Inotherwordstheyconstituteanincomplete setof
operators.Wewillseeinthenextsectionhowwecanputtogethera
complete (basis) setwhichwillallowustotreatcoupledevolutionsin
ashorthandsimilartothatusedforD(0)andD(1).Wemayuseasan
analogytheblocksachildwouldneedtobuildanynumberofcastles
ofdifferentshapesgiveninacatalog.Foragivencastlethechildmay
notneedtouseallthebuildingblocks,butheknowsthatnoneofthe
castleswouldrequireablockhedoesnothave.
5. PRODUCT OPERATORS (PO)
We willcalleachbuildingblockabasis operatorandwillgive
inTableII.1acompletesetofsuchoperatorsfortheAXsystem.The
bracket notations proposed by us will be defined as we explain how
thissetwasputtogether.
Table II.1 BasisOperatorsfor2Nuclei(I=1/2)
1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 0
[11] [ 1]
0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1
z
(
(
÷
(
= =
(
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 0
[1 ] [ ]
0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1
z zz
( (
( (
÷
( (
= =
( ( ÷ ÷
( (
÷
¸ ¸ ¸ ¸
68 Product Operator Treatment
0 1 0 0 0 0 0
1 0 0 0 0 0 0
[ 1] [ 1]
0 0 0 1 0 0 0
0 0 1 0 0 0 0
i
i
x y
i
i
÷ (
(
(
= =
( ÷
(
¸ ¸ ¸
(
(
(
(
(
¸
(
(
(
(
(
¸
(
(
(
(
(
¸
(
(
(
(
(
¸
(
(
(
(
(
¸
0
0 1 0 0 0 0 0
1 0 0 0 0 0 0
[ ] [ ]
0 0 0 1 0 0 0
0 0 1 0 0 0 0
i
i
xz yz
i
i
÷ (
(
(
= =
( ÷
(
÷ ÷
¸ ¸ ¸
0 0 1 0 0 0 0
0 0 0 1 0 0 0
[1 ] [1 ]
1 0 0 0 0 0 0
0 1 0 0 0 0 0
i
i
x y
i
i
÷ (
(
÷
(
= =
(
(
¸ ¸ ¸
0 0 1 0 0 0 0
0 0 0 1 0 0 0
[ ] [ ]
1 0 0 0 0 0 0
0 1 0 0 0 0 0
i
i
zx zy
i
i
÷ (
(
÷
(
= =
(
(
÷ ÷
¸ ¸ ¸
0 0 0 1 0 0 0
0 0 1 0 0 0 0
[ ] [ ]
0 1 0 0 0 0 0
1 0 0 0 0 0 0
i
i
xx xy
i
i
÷ (
(
÷
(
= =
(
(
¸ ¸ ¸
0 0 0 0 0 0 1
0 0 0 0 0 1 0
[ ] [ ]
0 0 0 0 1 0
0 0 0 1 0 0 0
i
i
yx yy
i
i
÷ ÷ (
(
(
= =
( ÷
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
These product operators have been introduced by Ernst and coworkers
(see O.W.Sörensen, G.W.Eich, M.H.Levitt, G.Bodenhausen, and
R.R.ErnstinProgress in NMR Spectroscopy, 16,1983,163192,and
The PO Formalism 69
references cited therein). The operators we use are multiplied by a
factorof2inordertoavoidwriting1/2somanytimes.
Each basis operatorisaproductoftwofactors,oneforeachof
the two nuclei (hence, the name "product operator"). The factor cor
responding to a given nucleus may be one of its own angular
momentum components multiplied by two (2I
x
, 2I
y
, 2I
z
) or the unit
matrix.
For example in the product operator [zz] the first factor is 2I
zA
andthesecond,2I
zX
.Proof:
1 0 0 0 1 0 0 0 1 0 0 0
0 1 0 0 0 1 0 0 0 1 0 0
0 0 1 0 0 0 1 0 0 0 1 0
0 0 0 1 0 0 0 1 0 0 0 1
( ( (
( ( (
÷ ÷
( ( (
× =
( ( ( ÷ ÷
( ( (
÷ ÷ ( ( (
¸ ¸ ¸ ¸ ¸ ¸
2 2
zA zX
[ ] I I zz × = (II.19)
Anotherexample:
 
0 1 0 0
1 0 0 0
[ 1] 2 2
0 0 0 1
0 0 1 0
xA xA
x I I
(
(
(
= = =
(
(
(
¸ ¸
1 (II.20)
ThebasissetinTableII.1allowsusnowtowrite(II.18)inshorthand
because we recognize that the third term in (II.18) contains the
productoperator[zy]andthefifthtermcontains[zx].Thus,
(2) ( 2 )[ 1] ( / 2 ) [1 ] ( / 2 ) [ ] D p N z q N cC y q N sS = ÷ + ÷ zy
( / 2 ) [1 ] ( / 2 ) [ ] q N sC x q N cS zx ÷ ÷ (II.21)
If we were to continue now to transform into product operators (PO)
allthesubsequentdensity matrices ofHETCORwewould,ofcourse,
beabletodoit,butthiswoulddousnogood.Thereal advantage will
consistinfindingawaytogofromonePOtothenextPO
70 Product Operator Treatment
without using matrices. There is a small price to pay for this
advantage, namely learning a few rules which show how to obtain a
newPOrepresentationafterpulses or evolutions.Itwillbeseenlater
that the PO advantage is much more important when we have to
handlesystemsofmorethantwospins.
6. PULSE EFFECTS (ROTATIONS) IN THE
PRODUCT OPERATOR FORMALISM
The great advantage of expressing the density matrix in terms
of product operators is found in the dramatic simplification of
calculationsneededtodescribepulseeffects(rotations).Letus illus
tratethisbyafewexamples.
(1) 90xXpulseappliedtoD(0):
90
( / 2 )[ 1] ( / 2 )[1 ] ( / 2 )[ 1] ( / 2 )[1 ]
xX
p N z q N z p N z q N y ÷ ÷ ÷÷÷÷÷ +
D(0) D(1)
This PO operation can be readily visualized in vector representation.
Indeed, looking at Figure II.2a we see that, while the angular
momentumofXmoves from ÷ zto+ y(90
o
rotation),thevectorof
Aremainsunaffected.
Letthevectorrepresentationguide us nowtowriteanotherPO
operation(seeFigureII.2b).
(2) 90xApulseappliedtoD(0):
90
( / 2 )[ 1] ( / 2 )[1 ] ( / 2 )[ 1] ( / 2 )[1 ]
xA
p N z q N z p N y q N z ÷ ÷ ÷÷÷÷+ ÷
D(0) D(1)
By following the same procedureinexamples3to5wefindout
that the product operators after any rotation can be written by
changing the labels x,y,z, of the affected nucleus according to the
rotationwhichtookplaceinthevectorrepresentation. Of course, the
unitmatrix(label"1")alwaysstaysthesame.
The PO Formalism 71
(3) 90yAX(nonselective)pulseappliedtoD(0):
90
( / 2 )[ 1] ( / 2 )[1 ] ( / 2 )[ 1] ( / 2 )[1 ]
yAX
p N z q N z p N x q N x ÷ ÷ ÷÷÷÷÷ ÷
D(0) D(1)
(4) 90xAappliedtoD(1)above:
90
( / 2 )[ 1] ( / 2 )[1 ] ( / 2 )[ 1] ( / 2 )[1 ]
xA
p N x q N x p N x q N x ÷ ÷ ÷÷÷÷÷ ÷
(Nochange,whatsoever)
(5) 90yAappliedtoD(1)above:
90
( / 2 )[ 1) ( / 2 )[1 ] ( / 2 )[ 1] ( / 2 )[1 ]
yA
p N x q N x p N z q N x ÷ ÷ ÷÷÷÷+ ÷
ThevalidityofthisapproachisdemonstratedinAppendixE.
Manypulsesequencescontainrotationsotherthan90
o
or180
o
.
We now proceedtoapplyourvectorruleforanarbitraryangleD(see
FigureII.2c).ThePOrepresentationofthisrotationis
( / 2 )[ 1] ( / 2 )[1 ] ( / 2 )[ 1]
( / 2 )([1 ]cos [1 ]sin )
xX
p N z q N z p N z
q N z y
o
o o
÷ ÷ ÷÷÷÷÷
÷ ÷
Afewmoreexamplesofrotationsaregivenbelow.Thistime
weignorethefactorsp/2Norq/2N.
90
[ ] [ ]
yA
zz xz ÷÷÷÷
90
[ ] [ ]
yX
zz zx ÷÷÷÷
90
[ ] [ ]
xA
zz yz ÷÷÷÷÷
180
[ ] [ ]
yA
xy x ÷÷÷÷÷ y
90
[1 ] [1 ]
xA
y y ÷÷÷÷
[ ] [ ]cos [ ]sin
yA
zz zz xz
o
o o ÷÷÷÷ +
72 Product Operator Treatment
90xX
z
y
x
z
y
x
x
y
z
x
y
z
90xA
(p/2N)[z1]
(q/2N)[1z]
(p/2N)[z1]
+(q/2N)[1y]
(p/2N)[z1]
(q/2N)[1z]
+(p/2N)[y1]
(q/2N)[1z]
(p/2N)[z1]
(q/2N)[1z]cosD
+(q/2N)[1y]sinD
(p/2N)[z1]
(q/2N)[1z]
DxX
z
y
x
z
y
x
D
a
b
c
A
X
A
X
A
X
X
X
X
A
A
A
Figure II.2.POandvectorrepresentationofrotations.
The PO formalism 73
It mustbementionedatthistimethatonlyPOscontainingx, y,
or z for one spin and 1 for the other(s) represent magnetization
components alongthecorrespondingCartesianaxesandhaveavector
representation. Nevertheless,therotationappliedtoallotherPOscan
be treated in the same way as above, by considering separately each
factorintheproduct.
The great advantage over the density matrix formalism is that
we can apply this approach to systems larger than two spins without
the considerable increase in the computation volume (for CH
3
the
matrixis16x16,i.e.,ithas256elements).InanAMXsystem (three
spin 1/2nuclei):
90
[ ] [
yA
zzz xzz ÷÷÷÷ ]
AMX
180
[ ] [ ]
xM
xzz xzz ÷÷÷÷÷
180
[ ] [
xA
] xzz xzz ÷ ÷÷÷÷÷
Nonselective pulses affect morethanonenucleusinthesystem.
Forexample:
90
[ ] [ ]
xAX
zz yy ÷÷÷÷
90
[ ] [ ]
xAX
xz x ÷÷÷÷÷ y
]
90
[ ] [
yAM
zzz xxz ÷÷÷÷
For rotations D other than 90
o
or 180
o
, nonselective pulses
affecting n nuclei must be handled in n successive operations. For
instance, a nonselective pulse DxAX applied to the product operator
[zy]istreatedinthefollowingsequence:
[ ] [ ]cos [ ]sin
xA
zy zy yy
o
o o ÷÷÷÷ ÷
2 2
[ ]cos [ ]cos sin [ ]sin cos [ ]sin
xX
zy zz yy yz
o
o o o o o ÷÷÷÷ + ÷ ÷ o
Thesetwooperationsmaybeperformedinanyorder.
74 Product Operator Treatment
7. TREATMENT OF EVOLUTIONS IN THE
PRODUCT OPERATOR FORMALISM
As shown in Appendix F, the evolution of coupled spins is
conveniently treated in two steps. Step 1: we consider the system
noncoupled (chemical shift evolution only). Step 2: we calculate the
effectofcoupling.
Step 1 (shift evolution)
Ashiftevolutionisequivalenttoarotationaboutthe z axisby
anangleD=:t.Example:
shiftA
[ 1] [ 1]cos [ 1]sin
A A
x x t y ÷÷÷÷ O + O t
TheanalogywiththevectorrepresentationisshowninFig.II.3.
x x
y y
shift A
evolution
D
D=[x1] D=[x1] cosD + [y1] sinD
Figure II.3. PO and vector representation of a coupled evolution.
Theangle D=:
A
t.
Anotherexample:
shiftX
[ ] [ ]cos [ ]sin
X X
zy zy t zx t ÷÷÷÷ O ÷ O
Theruleofthumbforshiftevolutionis:
POafterevolution=(PObeforeevolution)cos:t+(PObefore
evolution in which x is replaced by y and y by ÷ x for the spin
affectedbyevolution)sin:t.Thelabels1andz areinvariant.
The PO formalism 75
If more than one nucleus in the system is subject to shift
evolution, these evolutions have to be treated as separate steps (the
orderisimmaterial).Example:
shiftA
[ ] [ ]cos [ ]sin
A A
xyz xyz t yyz t ÷÷÷÷ O + O
M
AMX
shift M
[ ]cos cos [ ]cos sin
[ ]sin cos [ ]sin sin
A M A
A M A M
xyz t t xxz t t
yyz t t yxz t t
÷÷÷÷ O O ÷ O O
+ O O ÷ O O
(II.22)
The X spin is represented by z in the POs. Therefore the "shift X"
doesnotbringanyfurtherchangein(II.22).
Withthenotations
(II.23)
cos cos ' cos "
sin sin ' sin "
A M
A M
t c t c t c
t s t s t s
O = O = O =
O = O = O =
X
X
]
therelation(II.22)becomes
shiftA, M,X
[ ] '[ ] '[ ] '[ ] '[ xyz cc xyz cs xxz sc yyz ss yxz ÷÷÷÷÷÷ ÷ + ÷
Onemoreexample:
shiftA
[ ] [ ] [ ] xyy c xyy s yyy ÷÷÷÷ +
shift M
'[ ] '[ ] '[ ] '[ ] cc xyy cs xxy sc yyy ss yxy ÷÷÷÷ ÷ + ÷
shift X
' "[ ] ' "[ ] ' "[ ] ' "[
' "[ ] ' "[ ] ' "[ ] ' "[ ]
cc c xyy cc s xyx cs c xxy cs s xxx]
sc c yyy sc s yyx ss c yxy ss s yxx
÷÷÷÷ ÷ ÷ +
+ ÷ ÷ +
Step 2 (J coupling evolution)
According to the rules presented in Appendix F the coupling
betweentwospinsisactiveonlywhen oneofthenucleiappearsinthe
PO with an x or y while the other nucleus is represented by z or 1.
Examples:
[xzz] couplings J
AM
andJ
AX
areactive,butJ
MX
isnot. ÷
AMX
[xyz] couplings J
AX
andJ
MX
areactive,butJ
AM
isnot. ÷
76 Product Operator Treatment
Anotherexample:
[xyy] nocouplingisactive ÷
1
Foreverycouplingthatisactive,thestep2ruleis:
PO after evolution = (PO before evolution) cosSJt + (PO before
evolutionwithxreplacedby y, yby ÷ x,1by z,and zby1)sinSJt.
Examples:
[ ] [ ] [ 1]
AX
J
xz C xz S ÷÷÷÷ + y
t
t
with
cos
sin
AX
AX
C J
S J
t
t
=
=
[ ] [ ] [ 1
AX
J
] xyz C xyz S yy ÷÷÷÷ +
'[ ] '[ 1] '[ 1] '[ ]
MX
J
CC xyz CS xx SC yy SS yxz ÷÷÷÷ ÷ + ÷
where
cos
sin
AX
AX
C J
S J
t
t
t
t
=
=
' cos
' sin
AM
AM
C J
S J
t
t
t
t
=
=
Combinationsofsteps1and2areillustratedbytwoexamples.
SystemAM[x1]
shift A
[ 1] [ 1] c x s y ÷÷÷÷ +
(II.24) [ 1] [ ] [ 1] [ ]
AM
J
cC x cS yz sC y sS xz ÷÷÷÷ + + ÷
SystemAMX
shift A
[ 11] [ 11] [ 11] x c x s y ÷÷÷÷ +
[ 11] [ 1] [ 11] [ 1]
AM
J
cC x cS yz sC y sS xz ÷÷÷÷ + + ÷
'[ 11] '[ 1 ] '[ 1] '[ ]
AX
J
cCC x cCS y z cSC yz cSS xzz ÷÷÷÷ + + ÷
'[ 11] '[ 1 ] '[ 1] '[ ] sCC y sCS x z sSC xz sSS yzz + ÷ ÷ ÷ (II.25)
Notationsforthelasttwoexamples:
cos cos ' cos
sin sin ' sin
A AM
A AM
c t C J t C J
AX
AX
t
s t S J t S J
= O = =
= O = = t
(II.26)
We notice that, in the case of the two spin system, a coupled
evolution doesnotsplitanyPOintomorethan4terms.Thisisdueto
thefactthatwhenbothshiftsareactivethecouplingisnot.
1
This seemingly surprising situation prompts an explanation. Product
operators as [xx], [xy], [xyy] have nonvanishing elements on the secondary
diagonal only (which represents zero and multiplequantum coherences).
ReferringtoFigureI.1weseethattheevolutionfrequencyforthedouble
quantum transition (1 ÷ 4) is (A+J/2)+(XJ/2) = X+A. The zeroquantum
transitionfrequency(2 3)isXA.NoneofthemdependsonJ. ÷
The PO formalism 77
8. REFOCUSING ROUTINES
We haveseeninthe2DHETCORsectionthatthe180xCpulse
caused the decoupling of carbon from proton. In other words, the
pulseappliedinthemiddle of the evolution time te,causedthesecond
half to compensate for the coupling effect of the first half. We call
this a "refocusing routine." The chemical shift evolution can also be
refocused if the pulse is applied on the nucleus that evolves. The
routine, as shown below, can be handled in the conventional way
(evolutionpulseevolution) but the partial results are fairly more
complicatedthanthefinalresult.
' '
180
We suggest here an efficientcalculationshortcutinwhichthe
entireevolutiontime, ', can beplacedeitherbeforeorafterthepulse
(ofcourse,thiscannotbedoneintheactualsequence).
180 180
' '
Duringthehypotheticaldelay, ',thefollowingrulesapply:
a)Onlyshiftsofthenucleinotaffectedbythe180
o
pulseare
takenintoaccountintheevolution'sinceallotherarerefocused.
b) The coupling between two nuclei is active if both or none
ofthemareaffectedbythe180
o
pulse.
Theaboverulesarevalidforsystemsofmspin1/2nuclei,part
of which may be magnetically equivalent. The 180
o
rotation is
supposed to occur about an axis in the xy plane (no offresonance
pulse).Thephaseofthepulsedoesnotaffectthevalidityoftherules
but it must beconservedwhen,inourcalculations,wemovethepulse
fromthemiddleoftheinterval' tooneofitsends. The rules above
aredemonstratedinAppendixH.
78 Product Operator Treatment
We now compare the conventional calculation with the short
cut.Forexample,weassumethatthedensitymatrixattime t(n)is
( ) '[ 1] '[1 ] D n p x q x = +
anditisfollowedby
/ 2 180 / 2 xA A ÷ ÷A
In the conventional way, i.e., evolution ÷ pulse ÷ evolution,
westartwiththefirstevolution,'/2.
( ) ' [ 1] ' [ 1] '[1 ]
shift A
D n p c x p s y q ÷÷÷÷ + + x
' [ 1] ' [ 1] ' '[1 ] ' '[1 ]
shift X
p c x p s y q c x q s y ÷÷÷÷ + + +
' [ 1] ' [ ] ' [ 1] ' [
J
] p cC x p cS yz p sC y p sS xz ÷÷÷ + + ÷
' ' [1 ] ' ' [ ] ' ' [1 ] ' ' [ ] ( 1) q c C x q c S zy q s C y q s S zx D n + + + ÷ = +
J
where
cos / 2 ' cos / 2 cos / 2
A X
c c C t = O A = O A = A
sin / 2 ' sin / 2 sin / 2
A X
s s S J t = O A = O A = A
The 180xA pulse affects only the first label in the POs (nucleus A),
changingthesignofyandzandleavingxunchanged.
180
( 1) ' [ 1] ' [ ] ' [ 1] ' [
xA
] D n p cC x p cS yz p sC y p sS xz + ÷÷÷÷ ÷ ÷ ÷
' ' [1 ] ' ' [ ] ' ' [1 ] ' ' [ ] ( 2) q c C x q c S zy q s C y q s S zx D n + ÷ + + = +
]
Thesecondevolution'/2iscalculatedasfollows
2 2
( 2) ' [ 1] ' [ 1] ' [ ] ' [
shift A
D n p c C x p csC y p c S yz p csS xz + ÷÷÷÷ + ÷ +
2 2
' [ 1] ' [ 1] ' [ ] ' [ ] p scC y p s C x p scS xz p s S yz ÷ + ÷ ÷
' ' [1 ] ' ' [ ] ' ' [1 ] ' ' [ ] q c C x q c S zy q s C y q s S zx + ÷ + +
2 2
' [ 1] ' [ 1] ' [ ] ' [ ]
shift X
p c C x p csC y p c S yz p csS xz ÷÷÷÷ + ÷ +
2 2
' [ 1] ' [ 1] ' [ ] ' [ ] p scC y p s C x p scS xz p s S yz ÷ + ÷ ÷
2 2
' ' [1 ] ' ' ' [1 ] ' ' [ ] ' ' ' [ ] q c C x q c s C y q c S zy q c s S zx + + ÷ +
2 2
' ' ' [1 ] ' ' [1 ] ' ' ' [ ] ' ' [ ] ( ) q s c C y q s C x q s c S zx q s S zy D + ÷ + + = int
This is an intermediate result, since we still have to consider the effect
of Jcoupling.Beforedoingso,wecombinethetermscontainingthe
The PO formalism 79
samePO.
2 2 2 2
( ) '( ) [ 1] '( ) [ ] D p c s C x p c s S yz = + ÷ + int
2 2
'( ' ' ) [1 ] 2 ' ' ' [1 ] q c s C x q c s C y + ÷ +
2 2
'( ' ' ) [ ] 2 ' ' ' [ ] q c s S zy q c s S zx ÷ ÷ +
We recognize the expressions for the sine and cosine of twice the
angle :
X
'/2,i.e.,:
X
'.
( ) ' [ 1] ' [ ] D p C x p S yz = ÷ int
' cos ( [1 ] [ ]) 'sin ( [1 ] [ ])
X X
q C x S zy q C y S + O A ÷ + O A + zx
]
Further,wecalculatetheeffectofJ.
2 2
( ) ' [ 1] ' [ ] ' [ ] ' [ 1
J
D p C x p CS yz p SC yz p S x ÷÷÷ + ÷ + int
2 2
' cos ( [1 ] [ ] [ ] [1 ])
X
q C x CS zy SC zy S + O A + ÷ + x
2 2
' sin ( [1 ] [ ] [ ] [1 ])
X
q C y CS zx SC zx S y + O A ÷ + +
'[ 1] ' cos [1 ] 'sin [1 ]
X X
p x q x q y = + O A + O A
We now show that this result can be obtained in just two lines
by using the shortcut. Following the rules described above, we first
applythe180xApulse,thenanevolution '(whereonlytheshiftXis
considered,whiletheshiftAandthecouplingJareignored).
180
( ) '[ 1] '[1 ]
xA
D n p x q ÷÷÷÷ + x
'[ 1] ' cos [1 ] 'sin [1 ]
shift X
X X
p x q x q y ÷÷÷÷ + O A + O A
The first term, representing the A magnetization, appears unchanged
because its evolution during the first delay '/2 has been undone
during the second '/2. The X magnetization has evolved with the
frequency :
X
duringthedelay 'butintheenditisnotaffectedbythe
Jcoupling. This is because its two components, fast and slow, have
undergoneachangeoflabelinthemiddleofthedelay '.
In a system of two nuclei(AandX)ifthepulseaffectsnucleus
A, only shift X is operative. Shift A and coupling J
AX
are refocused
(seeexampleabove).Ifthe180
o
pulseaffectsbothAandX,only the
coupling is operative. Both shifts arerefocused.Inasystemofmore
than two nuclei (e.g., AMX), if the pulse affects all nuclei, only the
couplings are active. If the pulse affects all nuclei except one (e.g.,
nucleusA),weseetheeffectofshiftAandof the couplings which do
notinvolveA,i.e.,J
MX
.IfthepulseaffectsonlynucleusA,allshifts
exceptAandthecouplingsinvolvingA(J
AM
, J
AX
)areactive.
80 Product Operator Treatment
9. PO TREATMENT OF 2DHETCOR: TWO SPINS (CH)
We consider again the sequence in Figure I.2 applied to a
system of two weakly coupled spin 1/2 nuclei A and X. The density
matrixatequilibrium(seeII.5)is:
(0) '[ 1] '[1 ] D p z q z = ÷ ÷
where
p'=p/2N
q'=q/2N
N=numberofstates=4
pandq havethesamemeaningasin(I.3)and(I.4).
90
(0) '[ 1] '[1 ]
xX
D p z q y ÷÷÷÷÷ + (II.27)
D(1)
Weapplythe"refocusingroutine"treatmenttothesegment
/ 2 180 / 2
e e
t xA t ÷ ÷
AsshowninSectionII.8thisroutinehasthe same effect as the 180xA
pulse followed by an evolution t
e
during which only the shift X is
active.ThecouplingAXisrefocusedbythe180xApulse.
180
(1) '[ 1] '[1 ]
xA
D p z q y ÷÷÷÷ +
( )
'[ 1] ' cos [1 ] ' sin [1 ]
e
t shift X
X e X e
p z q W t y q W t x ÷÷÷÷÷ + ÷ (II.28)
D(4)
A coupled evolution A
1
follows, which can be handled according to
therulesofSectionII.7with
1 1
1 1
' cos cos
' sin sin
X
X
c C J
s S J
t
t
= O A = A
= O A = A
shift A
(4) same D ÷÷÷÷
shift X
'[ 1] ' cos ( '[1 ] '[1 ]) 'sin ( '[1 ] '[1 ])
X e X e
p z q t c y s x q t c x s y ÷÷÷÷ + O ÷ ÷ O +
'[ 1] ' cos ( ' [1 ] ' [ ] ' [1 ] ' [ ])
J
X e
p z q t c C y c S zx s C x s S zy ÷÷÷ + O ÷ ÷ ÷
' sin ( ' [1 ] ' [ ] ' [1 ] ' [ ])
X e
q t c C x c S zy s C y s S z ÷ O + + ÷ x
D(5)
2DHETCOR 81
Since A
1
=1/2Jand SJA
1
= t/2, C=0and S=1
(5) '[ 1] ' cos ( '[ ] '[ ])
X e
D p z q t c zx s zy = + O ÷ ÷
(II.29) ' sin ( '[ ] '[ ])
X e
q t s zx c z ÷ O ÷ + y
Using the trigonometric relations for the sum of two angles
[see(A29)and(A30)]wecanrewriteD(5):
1 1
(5) '[ 1] '[ ](cos cos sin sin )
X e X X e X
D p z q zx t t = + O O A ÷ O O A
1 1
'[ ](cos sin sin cos )
X e X X e X
q zy t t ÷ O O A + O O A
(II.30)
1 1
'[ 1] '[ ]cos ( ) '[ ]sin ( )
X e X e
p z q zx t q zy t = ÷ O + A ÷ O + A
We calculatenowtheeffectsofthepulsesthreeandfour(inthe
POformalismitissimplertohandlethemseparately):
90
1 1
(5) '[ 1] '[ ]cos ( ) '[ ]sin ( )
xX
X e X e
D p z q zx t q zz t ÷÷÷÷ ÷ O + A ÷ O + A
D(6)
90
1 1
'[ 1] '[ ]cos ( ) '[ ]sin ( )
xA
X e X e
p y q yx t q yz t ÷÷÷÷÷ + O + A + O + A
D(7) (II.31)
Since no other r.f. pulse follows we can concentrate on those
terms which represent observable magnetization components. We
observenucleusA,thereforeweareinterestedintheproductoperators
[x1]and[y1]whichgiveM
xA
andM
yA
. Wearealsointerestedin[yz]
and [xz] which can evolve into [x1], [y1] during a coupled evolution.
All product operators other than the four mentioned above are
nonobservableterms(NOT).WecanrewriteD(7)as:
(II.32)
1
(7) '[ 1] '[ ]sin ( ) NOT
X e
D p y q yz t = ÷ + O + A +
The second term is important for the 2D experiment because it is
proton modulated (it contains the frequency :
X
). It is also enhanced
bypolarizationtransfer(i.e.,multipliedbyq'ratherthanp').
Thecoupledevolution'
2
isnecessarytorenderthe second term
observable. If the decoupled detection started at t(7), the [yz] term
wouldevolveintoacombinationof[yz]and[xz],noneofwhichis
82 Product Operator Treatment
observable.Theobservableterms[x1]and[y1]canderivefrom [yz]
onlyinacoupledevolution.
shift A
1
(7) '( [ 1] [ 1]) ' sin ( )( [ ] [ ])
X e
D p c y s x q t c yz s xz ÷÷÷÷÷ ÷ + O + A
shift X
same '( [ 1] [ ] [ 1] [ ])
J
p cC y cS xz sC x sS yz ÷÷÷÷ ÷÷÷÷ ÷ ÷ ÷
1
' sin ( )( [ ] [ 1] [ ] [ 1])+NOT
X e
q t cC yz cS x sC xz sS y + O + A (II.33)
D(8)
where
2
2 2
cos cos
sin sin
A
A
c C
s S
2
J
J
t
t
= O A = A
= O A = A
(II.34)
During the decoupled evolution that follows after t(8), the
productoperators[x1],[y1]willevolveintocombinationsof[x1],[y1]
while the product operators [xz], [yz] evolve into combinations of
[xz],[yz],i.e.,theywillremainnonobservable.Wecantherefore retain
only[x1],[y1]intheexplicitexpressionofD(8):
1
(8) '( [ 1] [ 1]) ' sin ( )( [ 1] [ 1])
X e
D p cC y sC x q t cS x sS y = ÷ ÷ + O + A
+ NOT (II.35)
Inordertomaximizetheprotonmodulated term, one selects for
'
2
the value 1/2J which leads to S = 1 and C = 0. This value of '
2
represents an optimum in the particular caseoftheAXsystem.Itwill
be shown in Section II.10 that for AX
2
and AX
3
(e.g., the methylene
andmethylcases)ashorter'
2
istobeused.For'
2
=l/2J:
1 2 2
(8) ' sin ( )( cos [ 1] sin [ 1])+NOT
X e A A
D q t x y = ÷ O + A O A + O A
(II.36)
The simplest way to describe the decoupled evolution t
d
(from
the point of view of the observable A) is a rotation of the transverse
magnetization M
TA
aboutthezaxis. At t(8)wehave(seeAppendixJ):
M
xA
(8)= (M
oA
/p')(coefficientof[x1]) ÷
=(q'/p')M
oA
sinO
X
(t
e
+A
1
)cosO
A
A
2
M
yA
(8)=(q'/p')M
oA
sinO
X
(t
e
+A
1
)sinO
A
A
2
M
TA
(8)=M
xA
(8)+iM
yA
(8)=(q'/p')M
oA
sinO
X
(t
e
+A
1
)exp(iO
A
A
2
) (II.37)
2DHETCOR 83
Theratio '/ ' /
X A
q p ¸ ¸ = representstheenhancementfactorthrough
polarizationtransfer.
By handling the decoupled evolution as a magnetization
rotationweget
(9) (8)exp( )
TA TA A d
M M i = O t
+ A (II.38)
1 2
( '/ ') sin ( ) exp[ ( )]
oA X e A d
q p M t i t = O + A O
This is in agreement with the result obtained in Part I through
DMcalculations.ThecalculationsrequestedbythePO approach are
somewhatlesscomplicatedthanthose oftheDMapproach.Thereal
advantage will be seen when we apply (see Section II.10) the PO
formalismtoanAX
2
andAX
3
case(e.g.,the2DHETCORofaCH
2
or
CH
3
).
10. PO TREATMENT OF 2DHETCOR: CH
2
AND CH
3
We extend thecalculationscarriedoutinsectionII.9toanAX
2
orAX
3
system (e.g.,amethyleneoramethyl).Thedensitymatrixat
equilibriumis:
(II.39)
2
3
(0) '[ 11] '([1 1] [11 ]) for AX
(0) '[ 111] '([1 11] [11 1] [111 ]) for AX
D p z q z z
D p z q z z z
= ÷ ÷ +
= ÷ ÷ + +
Instead of following the two cases separately, we use the "multiplet
formalism" introduced in Appendix L. The reader should get ac
quaintedwiththisformalism beforeproceedingfurther.
(0) ( '/ ){ 1} '{1 } D p n z q z = ÷ ÷ (II.40)
validforanyAX
n
system.
90
(0) ( '/ ){ 1} '{1 }
xX
D p n z q y ÷÷÷÷÷ + (II.41)
D(1)
AswedidinsectionII.9,wetreatthesegment / 2 180 / 2
e e
t xA t ÷ ÷
84 Product Operator Treatment
asa"refocusingroutine"andthisbringsusdirectlyfrom D(1)toD(4).
180
(shiftX)
(1) ( '/ ){ 1} '{1 }
( '/ ){ 1} ' cos {1 } ' sin {1 }
e
xA
t
X e X e
D p n z q y
p n z q t y q t x
o
o : :
(II.42)
D(4)
Withtheassumptionthat
1
1/ 2J ' (i.e.,SJ'
1
=S/2)wehave
1
( )
(4) ( '/ ){ 1} ' cos { } ' sin { }
J
X e X e
D p n z q t zx q t zy
'
o : :
1
( )
( '/ ){ 1} ' cos ( '{ } '{ })
' sin ( '{ } '{ })
X e
X e
p n z q t c zx s zy
q t c zy s zx
'
o :
:
shift X
(II.43)
D(5)
where c', s'havethesamemeaningasin(II.29),i.e.,
1 1
' cos ; ' sin
X X
c s : ' : '
Using again the trigonometric relations for the sum of two
anglesaswedidin(II.30)werewriteD(5)as:
1 1
(5) ( '/ ){ 1} '{ }cos ( ) '{ }sin ( )
X e X e
D p n z q zx t q zy t : ' : '
(II.44)
90
1 1
(5) ( '/ ){ 1} '{ }cos ( ) '{ } sin ( )
xX
X e X e
D p n z q zx t q zz t o : ' : '
D(6)
90
1 1
(6) ( '/ ){ 1} '{ }cos ( ) '{ } sin ( )
xA
X e X e
D p n y q yx t q yz t o : ' : '
D(7) (II.45)
1
(7) ( '/ ){ 1} '{ }sin ( ) NOT
X e
D p n y q yz t : ' (II.46)
Uptothispointwehavefollowedstepbystepthe calculations
in Section II.9, while formally replacing [ ] by { } and using p'/n
insteadofp'. This procedureisalwaysvalidforrotations(pulses)and
inthiscaseitwasallowedforevolutionsasstatedinAppendixL,rule
#4.
For the coupled evolution '
2
we can concentrate on the
observableterms{x1},{y1}onlyandtakeadvantageoftheexception
2DHETCOR 85
statedinAppendixL,rule#5.
(II.47)
2
1 1
1
(7) ( '/ )( { 1} { 1})
' sin ( )( 1 { 1}) NOT
n n
n n
X e
D p n sC x cC y
q t cSC x sSC y
'
o
: ' { }
D(8)
n=numberofmagneticallyequivalentXnuclei(e.g.,number
ofprotonsinCH
n
).
2 2
2 2
cos cos
sin sin
A
A
c C
s S
J
J
S
S
: ' '
: ' '
Inordertoseparatetheeffectofshift(cands)andcoupling(CandS)
werewriteD(8)as
1
1
(8) ( '/ ) ( { 1} { 1}) ' sin ( ) ( { 1} { 1})
n n
X e
D p n C c y s x q t SC c x s y
: '
(II.48)
Here again the second term is the true 2D signal while the first one
generates axial peaks in the 2D picture since it does not contain the
frequency :
X
.
The value '
2
= 1/2J, which implies S = 1 and C = 0, is not
suitable anymore because it nulls the useful 2D signal for any n >1.
Wewilldiscusslatertheoptimumvalueof'
2
.
Inwritingthemagnetizationcomponentswehavetofollowthe
procedurestatedasrule#6inAppendixL.
M
xA
(8)= (nM
oA
/p')(coefficientof{x1})
1
2 1
sin ( '/ ') sin ( ) cos
n n
oA A oA X e A
M C nM q p SC t
: ' : ' : '
2
2
'
2
'
2
'
M
yA
(8)= (nM
oA
/p')(coefficientof{y1})
1
2 1
cos ( '/ ') sin ( )sin
n n
oA A oA X e A
M C nM q p SC t
: ' : ' :
M
TA
(8)=M
xA
(8)+iM
yA
(8)
1
2 1
exp( ) ( '/ ') sin ( ) exp( )
n n
oA A oA X e A
iM C i nM q p SC t i
: ' : ' :
1
1
[ ( '/ ') sin ( )]exp( )
n n
oA X e A
M iC n q p SC t i
: ' : (II.49)
86 Product Operator Treatment
Thedecoupledevolutiont
d
duringwhichthedetectiontakesplaceis
treatedthesamewayitwasdoneinII.9,asarotationaboutOz.
(9) (8)exp( )
TA TA A d
M M i : t
)] '
1
1 2
[ ( '/ ') sin ( )]exp[ (
n n
oA X e A d
M iC n q p SC t i t
: ' :
(II.50)
Theenhancementfactorofthe2Dtermis
1
( '/ ')
n
n q p SC
.
Now wecandiscusstheoptimumvalueof'
2
.InFigureII.4thevalue
of the product nSC
n1
isplottedversus'
2
Jforn=1,2and3.The
optimum '
2
valuesare:
2
1 ( ) 0.5/ n CH o ' J
J
J
(II.51)
2 2
2 ( ) 0.25/ n CH o '
3 2
3 ( ) 0.196/ n CH o '
A good compromise is '
2
= 0.3/J for which all three
expressions S, 2SC, and 3SC
2
have valuesexceeding0.8.Thebad
news is that this '
2
value does not cancel the axial peak, represented
bytheterm iC
n
in(II.50).
Figure II.4. Dependence of the factor nSC
n1
(S for CH, 2SC for
CH
2
,and3SC
2
forCH
3
)on'
2
J.
INEPT 87
11. PO TREATMENT OF A POLARIZATION
TRANSFER
SEQUENCE: INEPT (INSENSITIVE NUCLEI
ENHANCEMENT BY POLARIZATION TRANSFER)
WITH DECOUPLING
We discuss first the decoupled INEPT sequence shown in
Figure II.5. Its goal, an increased sensitivity of
13
C spectra, is
achieved in two ways: by increasing the peak intensities for the
protonated carbons, and by allowing a larger number of scans in a
givenexperimenttime.
t
d
t(0) t(1) t(2) t(3) t(4) t(5) t(6) t(7)
180xH 90xH
90xC 180xC
Decouple
90yH
H
C
13
1
W W '
Figure II.5TheINEPTsequence: 90 180 xH xCH t t ÷ ÷ ÷
90 90 yH xC A ÷ ÷ ÷ A ÷ T
WetreattheCH
n
casewithn=1,2or3.Thedensitymatrixat
thermalequilibriumis:
( '/ ){ 1} '{1 } D p n z q z = ÷ ÷ (II.52)
OneoftheadvantagesofINEPTisthatitallows fast scanning,
(limited by the proton relaxation only). In order to emphasize this
featurewewillassumethatonlytheprotonshavefullyrelaxedinthe
intervalbetweensequencesandwillwritetheinitialdensitymatrixas
(0) ( '/ ){ 1} '{1 } D p n z q z ì = ÷ ÷ (II.53)
where ìisarecoveryfactorforcarbon(0s ìs 1).
88 Product Opertator Treatment
Theeffectofthefirstpulseis
90
(0) ( '/ ){ 1} '{1 }
xH
D p n z q y ì ÷÷÷÷÷ + (II.54)
D(1)
SeeAppendixLforthemeaning of { } (multiplet formalism).
We treatnowtheportionfrom t(1)tot(4)asashiftrefocusingroutine
(see Section II.8). We will apply a nonselective 180xCH pulse
followed by a 2t evolution in which the coupling only is expressed
andthiswillbringustot(4).
180 2 ( .)
(1) ( '/ ){ 1} '{1 }
( '/ ){ 1} '{1 }cos 2 '{ }sin 2
xCH J coupl
D p n z q y
p n z q y J q zx J
t
ì
ì t t t t
÷÷÷÷÷+ ÷ ÷÷÷÷÷÷
÷÷÷ ÷ +
(II.55)
D(4)
Thenexttwopulseshavetobetreatedsuccessivelybecauseoneof the
termsinD(4)isaffectedbyboththeprotonandthecarbonpulse.
90
90
(4) ( '/ ){ 1} '{1 }cos 2 '{ }sin 2
( '/ ){ 1} '{1 }cos 2 '{ }sin 2
yH
xC
D p n z q y J q zz J
p n y q y J q yz J
ì t t t t
ì t t t t
÷÷÷÷ ÷ ÷
÷÷÷÷÷ ÷ +
D(5) (II.56)
After t(5) no pulse follows and we can concentrate on the
observableterms,keepinginmindthatourobservenucleusis
13
C.
(5) ( '/ ){ 1} '{ }sin 2 NOT D p n y q yz J ì t t = ÷ + + (II.57)
The second term is enhanced by polarization transfer and it does not
depend on ì. This means the pulse repetition rate is limited only by
the proton relaxation as far as the second term is concerned. The
optimum value for W is 1/4J which leads to sin 2 J t t = 1. With this
assumption:
(5) ( '/ ){ 1} '{ } NOT D p n y q yz ì = ÷ + + (II.58)
In D(5)thesecondtermisstillnotanobservable; hence, the necessity
of A.Usingrule#5inAppendixLweobtain:
(5) ( '/ ) ( { 1} { 1})
n
D p n C c y s x ì
A
÷÷÷÷ ÷
(II.59)
1
' ( { 1} { 1}) NOT
n
q SC c x s y
÷
+ ÷ ÷ +
D(6)
INEPT 89
Where
cos cos
sin sin
C
C
c C J
s S J
t
t
= O A =
= O A = A
A
A
The expression (II.59) has much in common with (II.48), with
thedifferencethattheprotonfrequency O
H
isnottobeseen.Thisis
not alarming since INEPT is not intended as a 2D sequence. Going
throughthesamestepsasfrom(II.48)to(II.50)weget:
(II.60)
1
(6) [ ( '/ ') ]exp( )
n n
TC oC C
M M i C n q p SC i ì
÷
= ÷ ÷ O
(II.61)
1
(7) [ ( '/ ') ]exp[ ( )]
n n
TC oC C d
M M i C n q p SC i t ì
÷
= ÷ ÷ O + A
We focus on thesecondterminthebrackets(polarizationtransferand
fast scanning). The optimum value of A is selected according to
Figure II.4 and relations (II.51), leading to . The
enhancementfactoristherefore
1
0.8
n
nSC
÷
>
0.8 /
H C
¸ ¸ > .
12. COUPLED INEPT
ThecoupledINEPT(FigureII.6)isusedforspectraediting.
t
d
t(0) t(1) t(2) t(3) t(4) t(5) t(6)
180xH 90xH
90xC 180xC
90yH
H
C
13
1
W W
Figure II.6ThecoupledINEPTsequence: 90 180 xH xCH t ÷ ÷
90 90 yH xC AT t ÷ ÷ ÷ ÷
90 Product Opertator Treatment
The magnetization at t(6) can be written by taking its ex
pressionfromtheprevioussequence(II.60)andreplacingAby t
d
:
1
(6) [ ( '/ ') ]exp( )
n n
TC oC C d
M M i C n q p SC i t ì
÷
= ÷ ÷ O (II.62)
with cos sin
d
C Jt S J
d
t t t = = (II.63)
Theresemblancewith(II.61)isonlyformal.In(II.61)wehad:
cos sin C J S J t t = A = A
and the detection time t
d
appeared only in the exponential factor
outside the brackets. Thesignalwasasinglet.In(II.62)thevariable
t
d
is also contained in C and S and the Fourier transform exhibits a
multiplet. In order to see how this multiplet looks like, we have to
discusstheexpression(II.62)forn=1,2,and3. We split M
TC
(6)into
twoterms
1
(6) ( '/ ') exp( ) exp( )
n n
TC oC C d oC C d
M M q p nSC i t iM C i t ì
÷
= ÷ O ÷ O
A B
M M = + (II.64)
and discussthesetwotermsseparately,whilekeepinginmindthatC
and Shavethemeaningsin(II.63).
A) Polarization enhanced multiplet (term M
A
)
WediscussseparatelytheCH,CH
2
,andCH
3
cases.
n=1(CHcase)
( '/ ') exp( )
A oC C d
M M q p S i t = ÷ O
Using(A28)wehave
exp( ) exp( )
2
d d
i Jt i Jt
S
i
t t ÷ ÷
=
andthisleadsto
( ) ( )
1
( '/ ')( )[ ]
2
C d C d
i J t i J t
A oC
M M q p e e
i
t t O + O ÷
= ÷ + (II.65)
ThisistheupdowndoubletofFigureII.7a.
INEPT 91
Foramethylene
n=2(CH
2
case)
( '/ ')2 exp( )
A oC C d
M M q p SC i t = ÷ O
Using(A36)wehave
exp(2 ) exp( 2 )
4
d d
i Jt i Jt
SC
i
t t ÷ ÷
=
and
( 2 ) ( 2 )
1
( '/ ')( )[ ]
2
C d C d
i J t i J t
A oC
M M q p e e
i
t O + O ÷
= ÷ +
t
d
(II.66)
This is a triplet with the central line missing and the other two lines
oneupandonedown(seeFigureII.7b).
n=3(CH
3
case)
2
( '/ ')3 exp( )
A oC C
M M q p SC i t = ÷ O
Weuse(A38)andobtain
( 3 ) ( )
( ) ( 3 )
3
( '/ ')( )[
8
]
C d C
C d C d
i J t i J
A oC
i J t i J t
M M q p e e
i
e e
t t
t t
O + O +
O ÷ O ÷
= ÷ ÷
+ +
d
t
(II.67)
This is the peculiar quartet in Figure II.7c: four lines of equal
intensities,twoupandtwodown.
B) Residual nonenhanced multiplet (term M
B
)
The term M
B
in (II.64) is smaller than M
A
(no polarization
enhancement and ì < 1). We will show that it represents a conven
tionalmultiplet.
n=1(CHcase)
exp( )
B oC C d
M iM C i t ì = ÷ O
92 Product Opertator Treatment
Using(A27)and i =1/iweobtain
( ) ( )
1
( )[ ]
2
C d C d
i J t i J t
B oC
M M e e
i
t
ì
O + O ÷
= +
t
(II.68)
theregulardoubletinFigureII.7d.
n=2(CH
2
case)
2
exp( )
B oC C d
M iM C i t ì = ÷ O
Using(A35)weobtainthetriplet
( 2 ) ( 2 )
1
( )[ 2 ]
4
C d C d C d
i J t i t i J t
B oC
M M e e e
i
t t
ì
O + O O ÷
= + + (II.69)
asinFigureII.7e.
n=3(CH
3
case)
3
exp( )
B oC C d
M iM C i t ì = ÷ O
Weuse(A37)andobtain
( 3 ) ( ) ( ) ( 3 )
1
( )[ 3 3 ]
8
C d C d C d C d
i J t i J t i J t i J t
B oC
M M e e e e
i
t t t
ì
O + O + O ÷ O ÷
= + + +
t
(II.70)
aregularlookingquartet(seeFigureII.7f).
Wenoticethatalltheexpressions(II.65)through(II.70) contain
the factor 1/i (or i) , indicating that the respective magnetizations
arealongthe yaxis.
÷
÷
When the term M
B
is not vanishingly small, it breaks the
symmetry of the multiplet, as showninFigureII.7(gthroughi).This
drawbackcanbeeliminatedbymeansofan appropriate phase cycling.
It is shown in Section II.13 that we have a similar situation with the
DEPT sequence and a two step phase cycling is sufficient to cancel
theresidualnonenhancedsignal.
INEPT 93
a
b
c
d
e
f
g
h
i
CH
CH
CH
2
3
J
J
J
J
2
Q
C
Q
C
Q
C
J
2
Figure II.7. Coupled INEPT; a,b,c ÷ Polarization enhanced
multiplet (term
A
M ); d,e,f ÷ Residual nonenhanced multiplet (term
B
M );g,h,i Actualspectrum ÷ (term )
A B
M M +
94 Product Operator Treatment
13. PO TREATMENT OF DEPT (DISTORTIONLESS
ENHANCEMENT POLARIZATION TRANSFER)
DEPT is a onedimensional sequence used as a tool for
unambiguous identification of the CH, CH
2
, and CH
3
peaks in a
proton decoupled
13
C spectrum. It shares with INEPT the advantage
of permittingafastrepetitionrate.Therecycletimehastobelonger
than the proton relaxation time but can be fairly shorter than the
carbon T
1
. The nonprotonated carbons will not show up in a DEPT
spectrum.
ThesequenceisshowninFigureII.8.
t(0) t(1) t(2) t(3) t(4) t(5)
1/2J 1/2J 1/2J
180xH 90xH T
90xC 180xC
t
d
t(6) t(7)
Decouple
yH
H
C
13
1
±
Figure II.8. The basic (onedimensional) DEPT sequence: 90xH
1/2J 180xH 90xC
÷
÷ ÷ ÷ 1/2J ÷ 180xC ÷ u ± yH ÷ 1/2J ÷ AT(dec
).
Theinitialdensitymatrixis
(0) ( '/ ){ 1} '{1 } D p n z q z ì = ÷ ÷ (II.71)
where O isarecoveryfactorforcarbon[see(II.53)]
90
(0) ( '/ ){ 1} '{1 }
xH
D p n z q y ì ÷÷÷÷÷ + (II.72)
D(1)
DEPT 95
Fortheevolutionweusethenotations
cos / 2 ' cos / 2 cos / 2 cos / 2 0
sin / 2 ' sin / 2 sin / 2 sin / 2 1
C H
C H
c J c J C J J
s J s J S J J
t t
t t
= O = O = = =
= O = O = = =
(II.73)
Intreatingtheevolution,theshiftandcoupling may be handled
inanyorder.Here,becauseof the particular values of CandS,weare
betteroffbystartingwiththecoupling.
coupl.
(1) ( '/ ){ 1} '{ }
J
D p n z q zx ì ÷÷÷÷÷ ÷
shift H
( '/ ){ 1} ' '{ } ' '{ } p n z q c zx q s zy ì ÷÷÷÷÷ ÷ ÷ (II.74)
D(2)
180
(2) ( '/ ){ 1} ' '{ } ' '{ }
xH
D p n z q c zx q s zy ì ÷÷÷÷÷ ÷ +
90
( '/ ){ 1} ' '{ } ' '{ }
xC
p n y q c yx q s yy ì ÷÷÷÷ + ÷ (II.75)
D(3)
The multiplet formalism { } can helpusonlysofar.Itdoesnot
apply to the coupled evolution of terms like {zx} or {yx} since this
coupled evolution is followed by some more pulses (cf. Rule #5 in
AppendixL).WehavetoconsiderseparatelytheCH,CH
2
,andCH
3
,
using the corresponding subscripts 1,2,3. For completeness, we will
alsoconsiderthecaseofthenonprotonatedcarbon(subscriptzero).
o
(3) '[ ] D p y ì =
1
(3) '[ 1] ' '[ ] ' '[ ] D p y q c yx q s yy ì = + ÷
2
(3) '[ 11] ' '([ 1] [ 1 ]) ' '([ 1] [ 1 ]) D p y q c yx y x q s yy y y ì = + + ÷ +
3
(3) '[ 111] ' '([ 11] [ 1 1] [ 11 ])
' '([ 11] [ 1 1] [ 11 ])
D p y q c yx y x y x
q s yy y y y y
ì = + + +
÷ + +
(II.76)
96 Product Operator Treatment
Theevolutionfrom t(3)tot(4)leadsto
(nocoupling)
shift C
o
(3) '( [ ] [ ]) (4) D p c y s x ì ÷÷÷÷ ÷ =
o
D
coupl.
1
(3) '[ ] '( '[ ] '[ ])
J
D p xz q c yx s yy ì ÷÷÷÷÷ + ÷
shift H 2 2
'[ ] '( ' [ ] ' '[ ] ' '[ ] ' [ ]) p xz q c yx c s yy s c yy s yx ì ÷÷÷÷÷ + + ÷ +
'[ ] '[ ] p xz q yx ì = ÷ +
shift C
1
'( [ ] [ ]) '( [ ] [ ]) (4) p c xz s yz q c yx s xx D ì ÷÷÷÷÷ + + ÷ =
InprocessingtheevolutionofD
2
(3) we havetotreatseparately
thecouplingofthecarbonwiththefirstandwiththesecondproton.
cpl AX1
2
(3) '[ 1] ' '([ 1] [ ]) ' '([ 1] [ ]) D p xz q c yx xzx q s yy xzy ì ÷÷÷÷÷ + ÷ ÷ ÷
cpl AX2
'[ ] ' '( [ ] [ ]) ' '([ ] [ ]) p yzz q c xxz xzx q s xyz xzy ì ÷÷÷÷÷÷ + ÷ ÷ ÷ ÷
shift H 2
'[ ] ' ' ( [ ] [ ]) ' ' '( [ ] [ ]) p yzz q c xxz xzx q c s xyz xzy ì ÷÷÷÷÷ + ÷ ÷ + ÷ ÷
2
' ' '( [ ] [ ]) ' ' ([ ] [ ] q s c xyz xzy q s xxz xzx ÷ ÷ ÷ ÷ + )
shift C
'[ ] '([ ] [ ]) '( [ ] [ ]) p yzz q xxz xzx p c yzz s xzz ì ì = ÷ ÷ + ÷÷÷÷÷ ÷
' ([ ] [ ]) ' ([ ] [ ]) q c xxz xzx q s yxz yzx ÷ + ÷ + D
2
4 ( )
We were allowed to handle the evolution of both protons in one step
only because none of the POs had x or y for both protons, i.e., only
oneprotonwasaffectedbytheevolutionineachPO.
Similar calculations will produce D
3
(4). Summarizing the
resultsatt(4)wehave:
o
(4) '( [ ] [ ]) D p c y s x ì = ÷
1
(4) '( [ ] [ ]) ' [ ] ' [ ] D p c xz s yz q c y x q s xx ì = ÷ ÷ + ÷ (II.77)
2
(4) '( [ ] [ ]) ' ([ ] [ ]) ' ([ ] [ ]) D p c yzz s xzz q c xxz xzx q s yxz yzx ì = ÷ + ÷ + ÷ +
3
(4) '( [ ] [ ]) ' ([ ] [ ] [ ]) D p c xzzz s yzzz q c yxzz yzxz yzzx ì = + ÷ + +
' ([ ] [ ] [ ]) q s xxzz xzxz xzzx + + +
DEPT 97
The u ± y pulse is mathematically equivalent to a y u ± pulse.
Therefore,wewilltreatitasarotationabouttheyaxiswithalternate
signsofT. Wetakealsointoaccountthat
cos( ) cos ; sin( ) sin u u u ÷ = ÷ = ÷ u
cos( ) cos ; sin( ) sin u u u ± = ± = ± u
D
180
o o
(4) '( [ ] [ ]) (5)
xC
D p c y s x ì ÷÷÷÷ ÷ ÷ =
(theprotonpulsehasnoeffect).
180
1
(4) '( [ ] [ ]) ' [ ] ' [ ]
xC
D p c xz s yz q c y x q s xx ì ÷÷÷÷ ÷ + ÷ ÷
' cos ( [ ] [ ]) 'sin ( [ ] ' [ ] NOT
yH
p c xz s yz q c y z q s xz
u
ì u u
±
÷÷÷÷ ÷ + ± + +
=D
1
(5)
In the last calculation we have retained only the observable terms
([x1],[y1])and the potentially observable terms ([xz],[yz]). We have
relegated terms as [xx], [xy], [yx], [yy] to the NOT bunch (non
observableterms),asdescribedinAppendixK.
In processing D
2
(4)wehavetocalculatetheeffectoftheproton
pulse, which is neither 90
o
nor 180
o
, separately on the two protons
(seeendofSectionII.6).
180
2
(4)
'( [ ] [ ]) ' ([ ] [ ]) ' ([ ] [ ])
xC
D
p c yzz s xzz q c xxz xzx q s yxz yzx ì
÷÷÷÷
÷÷÷ + ÷ + + +
1
' cos ( [ ] [ ]) ' cos ( [ ] [ ])
'sin ( [ ] [ ]) NOT
yX
p c yzz s xzz q c xzx s yzx
q c xzz s yzz
u
ì u u
u
±
÷÷÷÷ + + ÷ +
± ÷ +
2 2
' cos ( [ ] [ ]) ' cos sin ( [ ] [ ])
'sin cos ( [ ] [ ]) NOT
yX
p c yzz s xzz q c xzz s yzz
q c xzz s yzz
u
ì u u u
u u
±
÷÷÷÷ + ± ÷
± ÷ +
2
' cos ( [ ] [ ]) 2 ' cos sin ( [ ] [ ]) NOT p c yzz s xzz q c xzz s yzz ì u u u = + ± ÷ +
=D
2
(5)
98 Product Operator Treatment
SimilarcalculationshavetobeperformedonD
3
(4)andthesituationat
t(5)is
o
(5) '( [ ] [ ]) D p c y s x ì = ÷ ÷
1
(5) ' cos ( [ ] [ ]) 'sin ( [ ] ' [ ] NOT D p c xz s yz q c y z q s xz ì u u = ÷ + ± + +
(II.78)
2
2
(5) ' cos ( [ ] [ ])
2 ' cos sin ( [ ] [ ]) NOT
D p c yzz s xzz
q c xzz s yzz
ì u
u u
= +
± ÷ +
+
]
3
3
2
(5) ' cos ( [ ] [ ])
3 ' cos sin ( [ ] [ ])
D lp q c xzzz s yzzz
q q q c yzzz s xzzz NOT
= ÷
± ÷ ÷
Follows now the last 1/2J coupled evolution. We will retain only the
observableterms,havingxoryforcarbonand1forallprotons.
shift 2 2
o
(5) '( [ ] [ ] [ ] [ ]) '[
C
D p c y cs x sc x s y p y ì ì ÷÷÷÷ ÷ + ÷ ÷ = ÷
'[ ] (6)
o
p y D ì = ÷ =
coupl.
1
(5) ' cos ( [ 1] [ 1]) 'sin ( [ 1] [ 1] NOT D p c y s x q c x s y ì u u ÷÷÷÷ ÷ ÷ ± ÷ + +
shift C 2 2
' cos ( [ 1] [ 1] [ 1] [ 1]) p c y cs x sc x s y ì u ÷÷÷÷ ÷ + ÷ ÷
2 2
'sin ( [ 1] [ 1] [ 1] [ 1]) NOT q c x cs y sc y s x u ± ÷ ÷ + ÷ +
1
' cos [ 1] ( 'sin [ 1]) NOT= (6) p y q x D ì u u = ÷ ÷ ± +
After performing similar calculatons for D
2
(5) and D
3
(5), we can
summarizetheresultsatt(6)asfollows
(6) '[ ]
o
D p y ì = ÷
1
(6) ( ' cos [ 1] ' sin [ 1]) NOT D p y q x ì u u = ÷ ± + (II.79)
2
2
(6) ( ' cos [ 11] 2 'sin cos [ 11]) NOT D p y q x ì u u u = ÷ ± +
3 2
3
(6) ( ' cos [ 111] 3 ' sin cos [ 111]) NOT D p y q x ì u u u = ÷ ± +
AsaremarkableachievementoftheDEPTsequence,wenotice
that no chemical shift (proton or carbon) is expressed in the density
matrixattime t(6),whentheacquisitionbegins.Wewillnothaveany
frequency dependent phase shift. This alone can justify the
"distortionless"claiminthenameofthesequence.
DEPT 99
The term containing O can be relatively small when a high
repetition rate is used. We are interested in the second term, which
doesnotcontainthefactorOandisalsopolarizationenhanced(hasq'
ratherthanp').
The first term can be edited out by phase cycling. The sinT
factor in the expression of the density matrix corresponds to the last
proton pulse (see Figure II.8) being applied along the +y and y
axis,respectively.Ifwetakeascan with the phase +yandsubtractit
from the one with phase
±
÷
÷ y, the first term is cancelled and we are
leftwith
1
(6) ' sin [ 1] NOT D q x u = +
2
(6) 2 ' sin cos [ 11] NOT D q x u u = + (II.80)
2
3
(6) 3 'sin cos [ 111] NOT D q x u u = +
The subtraction is performed by a 180
o
shift in the receiver
phase.Theoretically,atwostep phasecyclingisenough,inwhichthe
phaseofthelastprotonpulseis
÷ y +y
andthereceiverphaseis
0
o
180
o
Additionalphasecyclingiscommonlyusedtocancelradiofrequency
interferencesandtheeffectofpulseimperfections.
The nonprotonated carbons do not appear in the phasecycled
spectrum.ThediscriminationbetweenCH,CH
2
,andCH
3
isdoneby
running the sequence three times, with different values of the flip
angle T,namely90
o
,45
o
and135
o
.
WhenT=90
o
,thencosT=0,sinT =1and(II.80)becomes
D
1
(6)=q'[x1])+NOT
D
2
(6)=NOT
D
3
(6)=NOT
Thisisa
13
CspectruminwhichonlytheCHlinesappear. When Tis
slightly larger or smaller than 90
o
, a CH
2
will appear as a small
singlet, negative or positive, respectively. That is why DEPT is a
good method for calibrating the 90
o
proton pulse in a spectrometer
configuredforobservingcarbon.
100 Product Operator Treatment
WhenT=45
o
,cosT=1/ 2 ,sinT=1/ 2 and(II.80)becomes
D
1
(6)=(1/ 2 )q'[x1])+NOT
D
2
(6)=q'[x11]+NOT
D
3
(6)= (3/ 2 2) q'[x111])+NOT
AllCH,CH
2
,andCH
3
appearaspositivesinglets.
WhenT=135
o
,thencosT=1/ 2 ,sinT=1/ 2 and(II.80)
becomes
D
1
(6)=(1 2 / )q'[x1])+NOT
D
2
(6)= ÷ q'[x11]+NOT
D
3
(6)= (3/ 2 2) q'[x111])+NOT
Thisisthesamesituationasfor45
o
,butCH
2
peaksappearnegative.
We have discussed all the features of DEPT using the
expression of the density matrix at time t(6), when the acquisition
begins.The
13
Cmagnetization,whichisorientedalongxatt(6),will
precessduringtheacquisitionwiththeLarmor frequency correspond
ingtotherespectivelineandwillappearasasinglet.
Inprincipleonlythe90
o
andthe135
o
runsaresufficientforan
unambigous identification of the CH, CH
2
, and CH
3
peaks. The 45
o
run is necessary when one wants to do spectral editing. For the
nonprotonated carbons, a normal run is needed with a long recycle
time.
Modern instruments offer the possibility to edit DEPT spectra
in order to select only the peaks of one group (e.g., CH) while
eliminatingthepeaksoftheothertwogroups (CH
2
andCH
3
).Thisis
theoretically based on linear combinationsofthespectraobtainedwith
differentvaluesofT(45
o
,90
o
,135
o
).
Table II.2 contains the relative amplitudes of CH, CH
2
, and
CH
3
peaksforeachofthethreeangles.
DEPT 101
Table II.2.RelativepeakamplitudesintherawDEPTspectra.
Spectrum u CH CH
2
CH
3
A
45
o
1 2
(0.707)
1
( )
3 2 2
(1.06)
B
90
o
1 0 0
C
135
o
1 2
(0.707)
1
( )
3 2 2
(1.06)
Table II.3 shows the operations necessary to obtain spectrs of
only one of the three groups or all of them together (note that the
spectrumtakenat45
o
also shows thepeaksofallgroups,butnottheir
trueamplitudes).
Table II.3.LinearcombinationsoftherawDEPT spectra, necessary
inordertoobtainonlyoneofthethreegroupsorallofthemtogether.
Combination CH CH
2
CH
3
B 1 0 0
(A C)/2 ÷ 0 1 0
(A+C1.41B)/2.12 0 0 1
Sumoftheabove 1 1 1
Some instrument softwares make it possible to alter the theo
reticalcoefficientsinordertocompensateforhardwareimperfections.
102 Product Operator Treatment
14. PO TREATMENT OF APT
(ATTACHED PROTON TEST)
APT is probably the first sequence designed to identify the
numberofhydrogenatomsattachedtoeachcarbon in a decoupled
13
C
spectrum. The sequence is relatively simple and does not involve
proton pulses. The broadband proton decoupler is kept permanently
on,withtheexceptionofonespecific1/Jdelay.
Thesequencecanbecorrectlyanalyzedwithintheframeofthe
vectorrepresentation.HerewetreatitwiththePOformalism.The
sequenceisshowninFigureII.9.
t(0) t(1) t(2) t(3)
t
d
t(4) t(5)
1/J 1/J
90xC 180yC
Decouple
H
C
13
1
Decouple
Figure II.9. The APT sequence: 90xC 1/J 180yC 1/J
(decouple) AT(decouple)
Wewilltreatseparatelythe C, CH, CH
2
,andCH
3
systems,denoting
therespectivedensitymatriceswithsubscripts0to3.
(0) '[ ]
o
D p z
z
z
(II.81)
1
(0) '[ 1] '[1 ] D p z q
2
(0) '[ 11] '([1 1] [11 ]) D p z q z
3
(0) '[ 111] '([1 11] [11 1] [111 ]) D p z q z z z
APT 103
Sincenocoherentprotonpulseisappliedthroughoutthe
sequence,wecananticipatethattheprotonPOswillneverturninto
13
Cobservables.WecantreatthemasNOT(nonobservableterms).
Westartthereforewith
(0) '[ ]
o
D p z
1
(0) '[ 1] NOT D p z (II.82)
2
(0) '[ 11] NOT D p z
3
(0) '[ 111] NOT D p z
Anyhow, the proton components do not have a predictable behavior
duringthedelayinwhichthedecoupleristurnedon(seeFigureII.9).
90
(0) '[ ] (1)
xC
o o
D p y o D
1
D
D
(II.83)
90
1
(0) '[ 1] NOT= (1)
xC
D p y o
90
2 2
(0) '[ 11] NOT= (1)
xC
D p y o
90
3 3
(0) '[ 111] NOT= (1)
xC
D p y D o
Fortheevolution1/Jweusethenotations
cos / ; cos / cos 1
sin / ; sin / sin 0
C
C
c J C J J
s J S J J
S S
S S
:
:
shift
(1) '( [ ] [ ]) (2)
C
o o
D p c y s x o D
coupl.
1
(1) '[ 1] NOT D p y o
shift
1
'( [ 1] [ 1]) NOT= (2)
C
p c y s x D o
coupl. 1 coupl. 2
2
(1) '[ 11] NOT '[ 11] NOT
AX AX
D p y p y o o
shift
2
'( [ 11] [ 11]) NOT= (2)
C
p c y s x D o
coupl. 1 coupl. 2
3
(1) '[ 111] NOT '[ 111] NOT
AX AX
D p y p y o o
coupl. 3
'[ 111] NOT
AX
p y o
shift
3
'( [ 111] [ 111]) NOT= (2)
C
p c y s x D o
In(II.84)wesummarizetheresultsatt(2).Itisnotnecessary
104 Product Operator Treatment
tocarrytheNOTanyfarther.
(2) '( [ ] [ ])
o
D p c y s x
D
D
D
D
) D
y
y
(II.84)
1
(2) '( [ 1] [ 1]) D p c y s x
2
(2) '( [ 11] [ 11]) D p c y s x
3
(2) '( [ 111] [ 111]) D p c y s x
We observe that the density matrices for CH and CH
3
have a
minussign.Itcomesfromthefactthat,duringthe evolution 1/J,the
coupling to each proton reverses the sign (C = 1). This is exactly
whattheAPTismeanttodo.Thefollowingpulseanddelay are only
intended to refocus the shift evolution, in order to avoid frequency
dependentphaseshifts.
180
o o
(2) '( [ ] [ ]) (3)
yC
D p c y s x o
180
1 1
(2) '( [ 1] [ 1]) (3)
yC
D p c y s x o
180
2 2
(2) '( [ 11] [ 11]) (3)
yC
D p c y s x o
180
3 3
(2) '( [ 111] [ 111]) (3)
yC
D p c y s x o
Nowwehavethe1/Jcoupledevolution
shift 2 2
o o
(3) '( [ ] [ ] [ ] [ ]) '[ ] (4
C
D p c y cs x sc x s y p y o
Itworksthesamewayfortheotherthreecasesandatt(4)wehave
(4) '[ ]
o
D p
(II.84)
1
(4) '[ 1] D p
2
(4) '[ 11] D p y
3
(4) '[ 111] D p y
At t(4) the detection starts. All peaks will be singlets
(decoupledacquisition)butCHandCH
3
willbenegative. Admittedly,
thePOtreatmentislessinstructiveabouthowthis has been achieved
thanthevectorrepresentation.
Evenwiththesequencesthatcannotbe handled with the vector
representation alone, it may be instructive to follow the evolution of
the magnetization components as indicated by the density matrix
expressions.WehavedonethisinSection3.11ofPartI.
Math Reminder 105
APPENDIX A: MATH REMINDER
Complex numbers
A complex number
z x iy (A1)
can be graphically represented as in Figure A.1, where
E
x
y
Re
Im
z
z
Im is the imaginary axis
Re is the real axis
is the real part of x z
y
is the coefficient of the
imaginary part of z
z is the modulus
z
E is the argument of z
(absolute value) of
Figure A.1. Graphic representation of a complex number z = x+iy.
i 1 is the imaginary unit.
The number z is fully determined when either x and y or z and
E are known. The relations between these two pairs of variables are
(see lower triangle):
cos x z  = (A2)
sin y z  = (A3)
Thus, according to (A1),
cos sin (cos sin ) z z i z z i    = + = +  (A4)
Using Euler's formula [see (A11)(A16)], one obtains:
exp( ) z z i = (A5)
The complex number * exp( ) z x iy z i = ÷ = ÷ is called the complex
conjugate of z.
106 Appendix A
Elementary rotation operator
Consider a complex number r which has a modulus r = 1 and
the argument D :
r i exp( ) cos sin i o o = = + o (A6)
Multiplying a complex number such as
exp( ) z z i =
by r leaves the modulus of z unchanged and increases the argument by
D:
( i ia i
zr z e e z e
)   o +
= = (A7)
Equation (A7) describes the rotation of the vector Oz by an angle D
(see Figure A.2). We can call r, the elementary rotation operator.
z
rz
E
D
0
Figure A.2. Effect of the rotation operator r = exp(iD ) on the
complex number z = zexp(iE ).
Note: Although more complicated, the rotation operators in the
density matrix treatment of multipulse NMR are of the same form as
our elementary operator [cf.(B45)].
Math Reminder 107
Example 1. A ÷ 90
o
(clockwise) rotation (see Figure A.3)
Let E D 90 90
o o
;
Then, from (A4 and A6),
o o
(cos90 sin90 ) z z i i z = + =
i ÷
(A8)
(A9)
o o
cos( 90 ) sin( 90 ) r i = ÷ + ÷ =
The product
( ) zr i z i z = ÷ = (A10)
is a real number (its argument is zero).
E = 90
o
zr
z
D =  90
o
Figure A.3. Effect of the rotation operator .
( )
o
90 i o ÷ = ÷
Equation (A10) tells us that the particular operator ÷ i effects
a 90
o
CW (clockwise) rotation on the vector z. The operator +i would
rotate z by 90
o
CCW. Two consecutive multplications by i result in a
180
o
rotation. In other words, an i
2
operator ( 1) orients the vector
in opposite direction.
Example 2. Powers of i (the "star of i")
Since i represents a 90
o
CCW rotation, successive powers of i
are obtained by successive 90
o
CCW rotations (see Figure A.4).
108 Appendix A
i
1/2
i
3/2
i
5/2
i
7/2
i
2
, i
6
, ... i
o
, i
4
, i
8
, ...
i, i
5
, ...
i
3
, i
7
, ...
Figure A.4. The star of i.
Series expansion of e
x
, sin x, cos x, and e
ix
The exponential function describes most everything happening
in nature (including the evolution of your investment accounts). The
e
x
series is
e
x
= 1 + x + x
2
/2! + x
3
/3! + . . . (A11)
The sine and cosine series are:
sin x = x ÷ x
3
/3! + x
5
/5! ÷ x
7
/7! + . . . (A12)
cos x = 1 ÷ x
2
/2! + x
4
/4! ÷ x
6
/6! + . . . (A13)
The e
ix
series is:
e
ix
= 1 + ix ÷ x
2
/2! ÷ ix
3
/3! + x
4
/4! + ix
5
/5!. . . (A14)
Math Reminder 109
Separation of the real and imaginary terms gives
e
ix
= 1 ÷ x
2
/2! + x
4
/4! ÷ x
6
/6! + . . . (A15)
+ i(x ÷ x
3
/3! + x
5
/5! ÷ . . .)
Recognizing the sine and cosine series one obtains the Euler formula
(A16) cos sin
ix
e x i = + x
Matrix algebra
Matrices are arrays of elements disposed in rows and columns;
they obey specific algebraic rules for addition, multiplication and in
version. The following formats of matrices are used in quantum
mechanics:
11 12 1
21 22 2
1 2
. .
. .
. . . . .
. . . . .
. .
n
n
n n nn
a a a
a a a
A
a a a
(
(
(
( =
(
(
(
¸ ¸
Square matrix
 
11
21
11 12 1
1
. . ; .
.
n
n
a
a
A a a a A
a
(
(
(
( = =
(
(
(
¸ ¸
Row matrix Column matrix
Row and column matrices are also called row vectors or column
vectors. Note that the first subscript of each element indicates the row
number and the second, the column number.
Matrix addition
110 Appendix A
Two matrices are added element by element as follows:
11 12 13 11 12 13 11 11 12 12 13 13
21 22 23 21 22 23 21 21 22 22 23 23
31 32 33 31 32 33 31 31 32 32 33 33
a a a b b b a b a b a b
a a a b b b a b a b a b
a a a b b b a b a b a b
+ + + ( (
( (
+ = + +
( (
( ( + + +
¸ ¸ ¸ ¸ ¸
(
(
+
(
(
¸
)
Only matrices with the same number of rows and columns can be
added.
Matrix multiplication
In the following are shown three typical matrix multiplications.
a) Square matrix times column matrix:
11 12 13 11 11
21 22 23 21 21
31 32 33 31 31
a a a b c
a a a b c
a a a b c
( ( (
( ( (
× =
( ( (
( ( (
¸ ¸ ¸ ¸ ¸ ¸
c a i.e., c a
11 11 11 12 21 13 31
21 21 11 22 21 23 31
31 31 11 32 21 33 31
c a b a b a b
b a b a b
c a b a b a b
= + +
= + +
= + +
3
1 1
1
( 1, 2, 3
j jk k
k
b j
=
= =
_
Example:
1 2 3 1 14
4 5 6 2 32
7 8 9 3 50
( ( (
( ( (
× =
( ( (
( ( (
¸ ¸ ¸ ¸ ¸ ¸
Each element of the first line of the square matrix has been multiplied
with the corresponding element of the column matrix to yield the first
element of the product:
1 1 2 2 3 3 14 × + × + × =
b) Row matrix times square matrix:
Math Reminder 111
  
11 12 13
11 12 13 21 22 23 11 12 13
31 32 33
b b b
a a a b b b c c c
b b b
(
(
× =
(
(
¸ ¸

)
(
(
(
(
¸
b
i.e., c a
11 11 11 12 21 13 31
12 11 12 12 22 13 32
13 11 13 12 23 13 33
c a b a b a b
c a b a b a b
c a b a b a b
= + +
= + +
= + +
3
1 1
1
( 1, 2, 3
j k kj
k
b j
=
= =
_
c) Square matrix times square matrix:
11 12 13 11 12 13 11 12 13
21 22 23 21 22 23 21 22 23
31 32 33 31 32 33 31 32 33
a a a b b b c c c
a a a b b b c c c
a a a b b b c c c
( (
( (
× =
( (
( (
¸ ¸ ¸ ¸ ¸
3
1
jm jk km
k
c a
=
=
_
For instance, row 2 of the left hand matrix and column 3 of the right
hand matrix are involved in the obtaining of the element c
23
of the
product. Example:
0 1 0 0 0
1 1
1 0 1 0
2 2
0 1 0 0 0
i
i i
i
÷ (
(
(
(
× ÷ =
(
(
¸ ¸ ¸
(
(
¸
0 / 2 0
1
0 0 0 0 0 0
2
0 / 2 0
i i i i
i i i i
÷ ÷ (
(
=
(
( ÷ ÷
¸ ¸ ¸
/ 2
/ 2
(
(
(
(
¸
The product inherits the number of rows from the first (left)
matrix and the number of columns from the second (right) matrix. The
number of columns of the left matrix must match the number of rows
of the right matrix.
In general the matrix multiplication is not commutative:
112 Appendix A
AB BA = (A17)
It is associative:
( ) ( ) A BC AB C ABC = = (A18)
and distributive:
( ) A B C AB AC + = + (A19)
The unit matrix is shown below
 
1 0 0 0
0 1 0 0
0 0 1 0
0 0 0 1
(
(
(
=
(
(
¸ ¸
1 (A20)
It must be square and it can be any size. Any matrix remains
unchanged when multiplied with the unit matrix:
   
A A A × = × = 1 1 (A21)
Matrix inversion
The inverse A of a square matrix A is defined by the relation:
1
 
1 1
A A A A
÷ ÷
× = × = 1 (A22)
To find : A
1
1) Replace each element of A by its signed minor determinant.
The minor determinant of the matrix element a
jk
is built with the
elements of the original matrix after striking out row j and column k.
To have the signed minor determinant, one has to multiply it by 1
whenever the sum j+k is odd.
÷
2) Interchange the rows and the columns (this operation is
called matrix transposition)
3) Divide all elements of the transposed matrix by the determi
nant of the original matrix A.
Example:
Find the inverse of matrix A.
Math Reminder 113
1 2 1 1/ 2 2 / 2 1/ 2
1
2 0 2 2 / 2 0 2 / 2
2
1 2 1 1/ 2 2 / 2 1/ 2
A
(
(
= ÷ = ÷ (
(
÷ ÷
(
¸ ¸ ¸
(
(
(
(
(
¸
1) We replace a
11
by
22 23
32 33
0 2 / 2
0 (1/ 2) ( 2 / 2) ( 2 / 2) 1/ 2
2 / 2 1/ 2
a a
a a
= = × + ×
÷
=
This is the minor determinant obtained by striking out row 1 and
column 1 of the original matrix.
We replace a
12
by
21 23
31 33
2 / 2 2 / 2
1/ 2 1/ 2
a a
a a
÷
÷ = ÷
[( 2 / 2) (1/ 2) ( 2 / 2) (1/ 2)] 2 / 2 = ÷ ÷ × ÷ × =
and so on, obtaining:
1/ 2 2 / 2 1/ 2
2 / 2 0 2 / 2
1/ 2 2 / 2 1/ 2
(
(
÷ (
(
÷
(
¸ ¸
2) The transposition yields:
1/ 2 2 / 2 1/ 2
2 / 2 0 2 / 2
1/ 2 2 / 2 1/ 2
(
÷
(
÷ (
(
(
¸ ¸
3) Calculate the determinant of A:
det(A) = 0 + (1/4) + (1/4) ÷ 0 + (1/4) + (1/4) = 1
114 Appendix A
Divided by 1, the transposed matrix remains unchanged:
1
1/ 2 2 / 2 1/ 2 1 2 1
1
2 / 2 0 2 / 2 2 0 2
2
1/ 2 2 / 2 1/ 2 1 2 1
A
÷
(
÷ ÷
(
= ÷ = (
(
(
¸ ¸ ¸
(
(
÷ (
(
(
¸
Check:
 
1
A A
÷
× = 1
1 2 1 1 2 1
1 1
2 0 2 2 0 2
2 2
1 2 1 1 2 1
( (
÷
( (
÷ × ÷ ( (
( (
÷
( (
¸ ¸ ¸ ¸
 
4 0 0 1 0 0
1
0 4 0 0 1 0
4
0 0 4 0 0 1
( (
( (
= =
( (
( (
¸ ¸ ¸ ¸
1 =
Note: You will be pleased to learn that:
a) There is a shortcut for the inversion of rotation operator
matrices because they are of a special kind.
b) In our calculations we will need only inversions of rotation
operators:
( ) R R
1
Here is the shortcut:
1) Transpose R (vide supra)
2) Replace each element with its complex conjugate.
Example
Math Reminder 115
1 2 1
1
2 0 2
2
1 2 1
R
(
(
= ÷ (
(
÷
(
¸ ¸
1) Transpose:
1 2 1
1
2 0 2
2
1 2 1
(
÷
(
÷ (
(
(
¸ ¸
2) Conjugate: Because they are all real, the matrix elements remain
the same:
1
1 2 1
1
2 0 2
2
1 2 1
R
÷
(
÷
(
= ÷ (
(
(
¸ ¸
Note: This is the same matrix as in the previous example; its being a
rotation operator matrix, allowed us to use the shortcut procedure.
Another example:
1 0 0
0 1 0
1
0 1 0
2
0 0
i
i
R
i
i 1
(
(
(
=
(
(
¸ ¸
(1) Transpose: you obtain the same matrix
(2) Conjugate:
116 Appendix A
1
1 0 0
0 1 0
1
0 1 0
2
0 0
i
i
R
i
i
÷
÷
1
(
(
÷
(
=
( ÷
(
÷
¸ ¸
Note: The matrix resulting from the transposition followed by
complex conjugation of a given matrix A is called the adjoint matrix
A
adj
. For all rotation operators,
1 adj
R R
÷
= (A23)
In other words, our short cut for inversion is equivalent with finding
the adjoint of R [see (A23)].
When A = A
adj
we say that the matrix A is self adjoint or Hermitian. In a Hermitian
matrix, every element below the main diagonal is the complex
conjugate of its symmetrical element above the diagonal
(A24)
*
nm mn
d d =
while the diagonal elements are all real. The angular momentum, the
Hamiltonian and density matrix are all Hermitian (the rotation
operators never are).
The matrix algebra operations encountered in Part 1 of this
book are mostly multiplications of square matrices (density matrix and
product operators). Inversion is only used to find reciprocals of
rotation operators, by transposition and conjugation. Frequently used
is the multiplication or division of a matrix by a constant, performed
by multiplying or dividing every element of the matrix. The
derivative of a matrix (e.g., with respect to time) is obtained by taking
the derivative of each matrix element .
Trigonometric relations
Sum of squared sine and cosine
Math Reminder 117
2 2
sin cos 1 o o + = (A25)
Negative angles
sin( ) sin
cos( ) cos
o o
o o
÷ = ÷
÷ =
(A26)
Expressing sine and cosine in terms of exponentials
cos
2
i i
e e
o o
o
÷
+
= (A27)
sin
2
i i
e e
i
o o
o
÷
÷
= (A28)
Demo: Use Euler's formula (A16) e i cos sin
io
o o
±
= ±
Sum and difference of two angles
sin( ) sin cos cos sin o  o  o ± = ±  (A29)
cos( ) cos cos sin sin o  o  o ± = B  (A30)
Demo:
1
2
cos sin
cos sin
i
i
z e i
z e i
o

o o
 
±
= = +
= = ±
( )
1 1
(cos sin )(cos sin )
i i
z z e i i
o 
o o 
±
= = + ± 
(cos cos sin sin ) (sin cos cos sin ) i o  o  o  o = + ± B 
cos( ) sin( ) i o  o = ± + ± 
Angle 2D
sin 2 2sin cos o o = o (A31)
118 Appendix A
2 2 2
cos 2 cos sin 2cos 1 o o o o = ÷ = ÷ (A32)
Demo: Make E = D in (A29),(A30). Use (A25) for the last form.
Angle 3D
3
sin3 3sin 4sin o o = ÷ o (A33)
3
cos3 4cos 3cos o o = ÷ o (A34)
Demo: Make E=2D in (A29),(A30), then use (A31),(A32) and
eventually (A25).
Relations used for AX
2
systems
2 2
2
1 cos 2 2
cos
2 4
i i
e e
o o
o
o
÷
+ +
= =
+
(A35)
2 2
sin 2
cos sin
2 4
i i
e e
i
o o
o
o o
÷
÷
= = (A36)
Demo: (A35) is a corollary of (A32) and (A36) is a corollary of
(A31). Use (A27), (A28) to obtain the exponential form. Note
the 121 triplet structure in (A 35).
Relations used for AX
3
systems
3 3
3
cos3 3cos 3 3
cos
4 8
i i i
e e e e
i o o o
o o
o
÷ ÷
+ + +
= =
o
+
(A37)
3 3
2
sin3 3sin
cos sin
4 8
i i i i
e e e e
i
o o o
o o
o o
÷ ÷
+ + ÷
= =
o
÷
(A38)
Demo: (A37) is a corollary of (A34). Relation (A38) can be
obtained by rewriting (A33) as
sin sin sin ( cos ) sin cos sin 3 3 4 1 4
2 2
D D D D D D D
Note the 1331 quartet structure in (A37).
Relations used for AX systems
cos( ) cos( )
cos cos
2
o  o
o 
 ÷ + +
= (A39)
Math Reminder 119
cos( ) cos( )
sin sin
2
o  o
o 
÷ ÷ +
=

(A40)
cos( ) cos( )
sin sin
2
o  o
o 
÷ ÷ +
=

(A41)
sin( ) sin( )
sin cos
2
o  o
o 
÷ + +
=

(A42)
Demo: Introduce (A29) or (A30) in the second member of the
equalities above.
120 Appendix B
APPENDIX B: DENSITY MATRIX FORMALISM
Wave functions and density matrix
The densitymatrixisatoolusedtodescribethestateofaspin
ensembleaswellasitsevolution in time.Itallowsthepassagefrom
theprobabilistictreatmentofasystem ofafewspinstothestatistical
treatmentofalargeensembleofsuchsystems.
Since we areinterestedinthemagnetizationwewanttoexpress
thisobservableintermsofthewavefunctionĳ ofthesystem.Letus
concentrateononeofthenucleiinthesystem(e.g.,nucleusA). The x
componentofthemagneticmomentofnucleusAhasthe expectation
value:
xA xA A xA
I µ ¢ µ ¢ ¸ ¢ ¢ = = = (B1)
where I
xA
istheoperatorofthexcomponentoftheangularmomentum
ofnucleusAinthegivensystem. Forinstance,inanAXsystemthe
I
xA
matrixis
0 1 0 0
1 0 0 0
1
0 0 0 1 2
0 0 1 0
(
(
(
(
(
¸ ¸
[see(C12)]
Inordertocalculatethemacroscopic magnetization, we have to
taketheaverage(denotedbyabar)overthewholeensemble:
o o xA xA A xA
M N N I µ ¸ ¢ ¢ = = = (B2)
where N
o
is the number of systems per unit volume, equal to the
number of Aspinsperunitvolume.Similarequationscanbewritten
foreverycomponentandforeverynucleusinthesystem.
In the Schrödinger representation I
xA
is a time independent
operator, therefore the time dependence of M
xA
is contained in the
wavefunction¢ofeachsystem.This,inturn,maybeexpressedasa
linearcombinationoftheeigenstates n ofthesystem:
Density Matrix Formalism 121
1
N
n
n
c n ¢
=
=
_
N=numberofquantumstatesofthesystem
Hereagainweobservethattheeigenfunctions n aretimeindepend
ent (solutions of the time independent Schrödinger equation), so the
time dependence is contained only in the coefficients c
n
. In order to
introducethesecoefficientsintheexpression(B2),weput
xA
I ¢ ¢
inmatrixform.The"ket" ¢ isacolumnmatrix:
1
2
.
.
n
c
c
c
¢
(
(
(
( =
(
(
(
¸ ¸
The"bra" ¢ isarowmatrix
* * *
1 2
. .
n
c c c ¢ ( =
¸ ¸
TheangularmomentumoperatorI
xA
isanNby Nsquarematrix.
11 12 1
21 22 2
1 2
. .
. .
. . . . .
. . . . .
. .
N
N
N N NN
I I I
I I I
I I I
(
(
(
(
(
(
(
¸ ¸
Thesubscript"xA"hasbeenomitedtosimplifythewriting.
Using the expressions for ¢ , I
xA
, and ¢ on the previous
page,weobtain:
122 Appendix B
xA
I ¢ ¢
* * *
1 2
. .
N
c c c ( =
¸ ¸
11 12 1 1
21 22 2 2
1 2
. .
. .
. . . . . .
. . . . . .
. .
N
N
N N NN N
I I I c
I I I c
I I I
(
(
(
( × ×
(
(
(
¸ ¸
c
(
(
(
(
(
(
(
¸ ¸
*
nm m n
1
2
* * * *
1 2
. . .
.
m m
m
m m
m
n n nm m
n m n m
N m m
m
I c
I c
c c c c I c I c c
I c
(
(
(
(
(
(
(
(
(
( ( = × = =
¸ ¸
(
(
(
(
(
(
(
(
(
(
¸ ¸
_
_
__ __
_
(B4)
Wehaveobtainedacompactexpressionof
xA
I ¢ ¢
In order to introduce it intheexpression(B2)ofthemagnetizationwe
have to take its average over the whole ensemble of systems. The
matrix elements I
mn
are characteristic for the system. They are
identicalforallthesystems in ourmacroscopicensemble.Therefore
in (B4)onlytheproduct c c hastobeaveragedovertheensemble
andweget
m n
*
Density Matrix Formalism 123
*
o xA A nm m n
n m
M N I c ¸ = c
__ (B5)
where I
nm
are the matrix elements of the operator I
xA
. The only time
variableelementsin(B5)aretheaveragedproducts
*
m n
c c .
ThereareN
2
suchproductswhich, arranged inasquaretable,formthe
densitymatrix:
11 12 1
21 22 2
1 2
. .
. .
. . . . . (B6)
. . . . .
. .
N
N
N N NN
d d d
d d d
D
d d d
(
(
(
( =
(
(
(
¸ ¸
with
*
mn m n
d c c = (B7)
Wenoticethat ,i.e.,DisaHermitianmatrix.
*
nm mn
d d =
Density matrix and magnetizations
Werewrite(B5)makinguseoftheexpression(B7)
*
o o xA A nm mn A nm nm
n m n m
M N I d N I ¸ ¸ = = d
__ __ (B8)
Relation (B8) represents the practical mode of calculating an
observable magnetization component (in our case M
xA
) when the
densitymatrix Disknown:
Multiply every matrix element of I
xA
with the complex conjugate
of the corresponding element of D and add all the products. Multiply
the sum by N
o
¸
A
. =
It is convenient to express the factor N
o
¸
A
in terms of the
equilibriummagnetization M
oA
:
=
124 Appendix B
2 2
o
o
( 1)
3
A
A
N I I B
M
kT
¸ +
=
=
o
(B9)
Note that M
oA
is always a positive quantity, the absolute value of the
equilibrium magnetization for nucleus A. For I = 1/2 the expression
(B9)becomes:
2 2
o
o
4
A
A
N B
M
kT
¸
=
=
o
(B10)
In(I.3)wehaveintroducedthequantity
o A
A A
B
h
p
kT kT kT
¸
v e
= = =
=
=
(B11)
related to the Boltzmann factorofnucleusA.Inaccordancewithour
signconvention(negative¸)thiscanberewrittenas
o A
B
p
kT
¸
= ÷
=
(B12)
and(B10)becomes
o
o
4
A
A
N p
M
¸
= ÷
=
Thefactor
o A
N ¸ = in (B8) can nowbewritteninthemoreconvenient
form
o
4
A
N
p
¸ = ÷ =
oA
M (B13)
FornucleusX(seeI.4)thefactoris
o o
4
X X
N M
q
¸ = ÷ =
Letusapplythe"recipe"forfindingthemagnetizationcomponentsto
thesystemAX(twospin1/2 nuclei). ThenumberofstatesisN=4and
the(Hermitian)densitymatrixhastherank4:
Density Matrix Formalism 125
11 12 13 14
21 22 23 24
31 32 33 34
41 42 43 44
d d d d
d d d d
D
d d d d
d d d d
(
(
(
=
(
(
(
¸ ¸
where and d
jj
=real(
*
kj jk
d d =
*
jj jj
d d = ).
The angular momentum components for the AX system are
givenin(C12)through(C15).Wehaveforinstance
1 0 0 0
0 1 0 0
1
0 0 1 0 2
0 0 0 1
zA
I
(
(
÷
(
=
(
(
÷
¸ ¸
(B14)
inwhichonlyfourmatrixelementsoutof16arenonvanishing.
Using(B8)and(B14)inthisparticularcaseweget:
33 11 22 44
4
2 2 2 2
zA oA
d d d d
M M
p
 
= ÷ ÷ + ÷

\ .
(
11 22 33 44
2
oA
) M d d d d
p
= ÷ ÷ + ÷ (B15)
Inthexdirection
0 1 0 0
1 0 0 0
1
(B16)
0 0 0 1 2
0 0 1 0
xA
I
(
(
(
=
(
(
¸ ¸
andthe"recipe"leadsto
126 Appendix B
( )
12 21 34 43
2
* * * *
xA oA
M M d d d d
p
= ÷ + + + (B17)
Inthesamewayweobtain
( )
12 21 34 43
2
* * * *
yA oA
i
M M d d d d
p
= ÷ + ÷ (B18)
It is always convenient to combine M
x
and M
y
in one complex
quantity,thetransversemagnetization
T x y
M M iM = + (B19)
Thisleadstothesimplifiedform
(
12 34
4
* *
TA oA
M M d d
p
= ÷ + ) (B20)
The magnetization components for the other nucleus of the
system,nucleusX,aregivenby
(
11 22 33 44
2
zX oX
) M M d d d d
q
= ÷ + ÷ ÷ (B21)
(
13 24
4
* *
TX oX
M M d d
q
= ÷ + ) (B22)
This is equivalent to calculating the trace (sum of diagonal
elements)oftheproduct I D × :
(
nm mn
n m
) I d Tr I D = ×
__
(B23)
The density matrix at thermal equilibrium
Atequilibriumthenondiagonalelementsarenull because of the
random phase distribution of the complex coefficients c
m
. We denote
with 
m
thephaseofthecomplexquantity c
m
:
exp( )
m m m
c c i = (B24)
Anondiagonalmatrixelementis
Density Matrix Formalism 127
 
*
exp ( )
mn m n m n m n
d c c c c i   = = ÷ (B25)
The phase difference 
m
÷ 
n
can have any value within 0 and 2t
with equal probability. The complex number exp[i(
m

n
)],
described as a vector in the complex plane, may be oriented in any
direction.Theaverageofamultitudeofsuchvectorsisnull.
÷
Thediagonalelementsarenotnullsince
m
÷ 
m
=0.
2
*
mm m m m
d c c c = = (B26)
In quantum mechanics
2
m
c is the probablity of finding thesystem
in the state m ; therefore d
mm
= P
m
is the population of this state.
Thedensitymatrixatequilibriumis
1
2
0 . . 0
0 . . 0
. . . . . (B27)
. . . . .
0 0 . .
N
P
P
D
P
(
(
(
( =
(
(
(
¸ ¸
where (normalizedpopulations). 1
n
P =
_
Evolution of the density matrix between pulses
Intheabsenceofther.f.excitationtheHamiltonian Haccepts
thekets n aseigenfunctions:
n
n E n = H (B28)
andtheSchrödingerequation
i t
c¢
¢
c
÷
=
=
H
becomes:
128 Appendix B
d
d
n
n n
c
n c E
i t
÷
=
_ _
=
n (B29)
Rearranging(B29)gives
d
0
d
n
n n
c
c E n
i t
(  
+ =

\ . ¸ ¸
_
=
(
(B30)
Due totheorthogonalityoftheeigenfunctions,(B30)issatisfiedonly
ifeachtermofthesumisnull:
d
0
d
n
n n
c
c E
i t
+ =
=
(B31)
Hence
d 1
d
n
n
c iE
c t
n
÷
=
=
(B32)
or
( )
d
ln
d
n
n
iE
c
t
÷
=
=
(B33)
Integrating(B33)yields:
ln
n
n
iE
c t C = ÷ +
=
(B34)
exp exp( )
n
n
iE
c t
÷  
=

\ .
=
C
C
(B35)
The integration constant C may be related to the value of c
n
at time
.Thisgives 0 t = (0) exp( )
n
c = and(B35)becomes
(0) exp
n
n n
iE
c c t
÷ 
=
\ .
=


(B36)
Knowing the evolution of all c
n
coefficients will allow us to predict
thetimevariationofthedensitymatrix,hencethatofthe
magnetization:
Density Matrix Formalism 129
( )
* *
(0) (0) exp
m n
mn m n m n
i E E
d c c c c t
÷ ÷  
= =

\ .
=
(0) exp( )
mn mn
d i t e = ÷ (B37)
We have demonstrated here the relation (I.13) used in the density
matrixtreatmenttodescribetheevolutionbetweenpulses.Thepopu
lations are invariable because E
m
÷ E
m
= 0 (relaxation processes are
neglectedthroughoutthisbook).
Effects of radiofrequency pulses
We havetofindthetimeevolutionofthedensitymatrixunder
a given Hamiltonian, as we did in the previous section, but there are
twothingsthatmaketheproblemmorecomplicated.
First, the Hamiltonian is now timedependent (radiofrequency
magneticfield).Thisproblemcanbecircumventedbydescribingthe
evolution of the system in a rotating frame, in which the rotating
magnetic field appears as an immobile vector B
1
, while the main
magneticfieldB
o
isreplacedby
o tr
B B e ¸ A = ÷
TheresultantofB
1
and'BistheeffectivefieldB
eff
(FigureB.1).
The field B
1
is usually much larger than 'B and the effective
fieldpracticallyisB
1
.TheHamiltonianintherotatingframeisthen
1 x
B I ¸ = = H (B38)
aswehaveassumedthatB
1
isappliedalongthex axisoftherotating
frame. For comparison, in the absence of the r.f. field, the Hamilto
nianintherotatingframeis
z
BI ¸ = A = H (B39)
whileinthelaboratoryframeithastheexpression
o z
B I ¸ = = H (B40)
130 Appendix B
x
y
z

B
1
B
eff
' B =B
o
 Z /  J
tr
Figure B.1. The effective magnetic field B
eff
in the rotating frame.
Ox, Oy = axes of the rotating frame ; Z
tr
= angular frequency of r.f.
transmitter(angularvelocityoftherotatingframe)
Now we come to the second difficulty which prevents us from
usingthesameapproachasintheprevioussection: the new Hamilto
nian (B38) does not have the kets n as eigenfunctions because we
have passed from B
0
to B
1
. We have to use a more general equation
whichdescribestheevolutionofDunderanyHamiltonian:
d
(
d
D i
D
t
= ÷
=
H H ) D (B41)
the demonstration of which is given separately in the following
section.Thesolutionof(B41)is:
( ) ( ) ( ) exp / (0) exp / D t i t D i t = ÷ = H = H (B42)
Thiscanbeverifiedbycalculatingthetimederivativeof(B42):
Density Matrix Formalism 131
( ) (
d d
exp / (0) exp /
d d
D
i t D i t
t t
(
= ÷
(
¸ ¸
= = H H )
( ) ( )
d (0)
exp / exp /
d
D
i t i t
t
(
+ ÷
(
¸ ¸
= = H H
( ) ( )
d
exp / (0) exp /
d
i t D i t
t
(
+ ÷
(
¸ ¸
= = H H
( ) ( ) exp / (0) exp / 0
i
i t D i t
÷
= ÷ = =
=
H
H H +
( ) ( ) exp / (0) exp /
i
i t D i t + ÷ = =
=
H
H H
( ) ( ) ( ) / / / i D D i i D = ÷ + = ÷ = = = H H H D H
In the particular case ofa strong r.f. field B
1
appliedalongthexaxis
oftherotatingframewehave,accordingto(B38):
1
/
x x
i t i B I t i I ¸ o = = = H (B43)
where
1
Bt o ¸ = istherotationangleofthemagnetizationaroundB
1
inthetime t(pulseduration).Relation(B42)becomes
( ) ( ) exp (0) exp
x x
D iI D iI o o = ÷ ÷
1
(0) R D R
÷
= (B44)
where R is the rotation operator [cf (A6)(A7)]; D(0) and D denote
the density matrix before and after the pulse. We have thus
demonstratedtherelation(I.8).
In order to get an explicit matrix expression for R we have to
calculate
exp( )
x x
R i I
o
o = (B45)
usingaseriesexpansionoftheexponential[see(A11)],
2 2 3 3
( ) ( )
1 . . .
2! 3!
x x
x x
i I i I
R i I
o
o o
o = + + + + (B46)
ThepowersofI
x
mayeasilybecalculatedifonenoticesthat
132 Appendix B
 
2
1
4
x
I
 
=

\ .
1 (B47)
0 1
1
1 0 2
x
I
(
=
(
¸ ¸
 
2
1 0
1 1
0 1 4 4
x
I
(
 
= =
 (
\ .
¸ ¸
1
3
0 1
1 1 1
2
1 0 4 8 8
x x x
I I I
(
 
= = =
 (
\ .
¸ ¸
 
4
1 0
1 1
0 1 16 16
x
I
(
 
= =
 (
\ .
¸ ¸
1
Ingeneral,forn=evenwehave:
 
1 0
1 1
0 1 2 2
n
x n n
I
(
 
= =
 (
\ .
¸ ¸
1 (B48)
andforn=odd
0 1
1 1
2
1 0 2 2
n
x n n x
I I
(
 
= =
 (
\ .
¸ ¸
(B49)
By using (C12) and (C14) one can verify that (B48) and (B49) are
alsotrueforI
xA
andI
xX
inatwospinsystemwithI=1/2.
Introducing (B48) and (B49) in (B46) and separating the even
andoddtermsgives:
2 4
1 0
( / 2) ( / 2)
1 . . .
0 1 2! 4!
x
R
o
o o ( (
= ÷ + ÷ ×
( (
¸ ¸ ¸ ¸
3 5
0 1
( / 2) ( / 2)
/ 2 . . .
1 0 3! 5!
i
o o
o
( (
+ ÷ + ÷ ×
( (
¸ ¸ ¸ ¸
(B50)
Recognizing the sine (A12) and cosine (A13) series expansions we
canwrite
Density Matrix Formalism 133
  ( )
1 0 0 1
cos sin cos sin 2
0 1 1 0 2 2 2 2
x x
R i i
o
o o o o ( (
= + = +
( (
¸ ¸ ¸ ¸
1 I
cos 0 0 sin
2 2
(
(
=
(
(
(
¸
0 cos sin 0
2 2
i
i
o o
o o
(
(
= +
(
(
(
¸ ¸ ¸
cos sin
2
sin cos
2 2
i
i
2
o o
o o
(
(
(
(
(
¸ ¸
(B51)
FornucleusAinanAXsystemtherotationoperatoris
cos sin 0 0
2 2
sin cos 0 0
2 2
0 0 cos sin
2
0 0 sin cos
2 2
x
i
i
R
i
i
o
o o
o o
2
o o
o o
(
(
(
(
(
=
(
(
(
(
(
(
¸ ¸
(B52)
If the pulse is applied along the y axis, relations similar to (B48),
(B49)apply:
 
1
forn=even
2
n
y n
I
 
=

\ .
1
(B53)
1
(2 ) forn=odd
2
n
y y n
I I
 
=

\ .
andweobtain
exp( ) cos [ ] sin (2 )
2 2
y y y
R i I i I
o
o o
o = = + 1 (B54)
Appendix C contains angular momentum components and
rotation operators in matricial form,foravarietyofspinsystemsand
pulses. The reader may checksomeofthoseresultsbymaking o
=90
o
or o=180
o
intherelationsabove.
If the radiofrequency field B
1
is applied along the ÷ x axis, it
has the same effect as a pulse along the +x axis, only the sense of
134 Appendix B
rotation is reversed (left hand instead of right hand rule). The result
ofsuchapulseisthereforearotationby ÷ oaroundOx:
( ) ( )
exp( ) cos [ ] sin (2 )
2 2
x x x x
R R i I i
o o
I
o o
o
÷ ÷
= = ÷ = ÷ 1 (B55)
It is possible to extend the DM treatment to pulses with any
phase (not only the four cardinal phases x, y, ÷ x, ÷ y) and/or off
resonancepulses(B
eff
doesnotcoincidewith B
1
).Wewillnotdiscuss
themherebecause,asshowninthesecondpartofthebook,itis more
convenient to handle them by means of the Product Operator
formalism(seeAppendixM).
Demonstratiom of (B41)
Inordertodemonstratethat
d
( )
d
D i
D D
t
= ÷
=
H H
we follow the procedure used by Slichter (see Suggested Readings).
Westartwiththe(timedependent)Schrödingerequation
i t
c¢
¢
c
÷
=
=
H
where
1
N
n
n
c n ¢
=
=
_
withtheobservationthat n arenotassumedtobeeigenfunctionsof
H.Combiningthelasttwoequationsgives
1 1
d
d
N N
n
n
n n
c
n c
i t
= =
÷
=
_ _
=
H n (B56)
Ifwepremultiplythisequationwiththebra m weget
Density Matrix Formalism 135
1 1
d
d
N N
n
n
n n
c
m n c m n
i t
= =
÷
=
_ _
=
H (B57)
The choice of normalized and orthogonal functions for the basis set
n implies
0 for m n m n = =
1 for m n m n = = (B58)
Ontheotherhand m H n isthematrixelement H
mn
inthematrix
representationoftheHamiltonian,so(B57)becomes
1
d
d
N
n
n mn
n
c
c H
i t
=
÷
=
_
=
(B59)
Ifweconsidernowtheproduct
*
jk j k
p c c = (B60)
itstimederivativewillbe
*
*
d d
d
d d d
jk j
k
k j
p c
c
c c
t t
= +
t
*
*
d
d
d d
j
k
k j
c
c
c c
t t
 
= +

\ .
*
*
1 1
N N
n jn k j n kn
n n
i i
c H c c c H
= =
( ÷ ÷   
= +

( 
\ . \

. ¸ ¸
_ _
= =
* * *
1 1
N N
j n kn n k jn
n n
i
c c H c c H
= =
 
= ÷

\ .
_ _
=
Thechangeofsigncomesfrom( ÷ i)
*
=i.
IfwetakeintoaccountthatHisHermitian(H
*
kn
=H
nk
)weget
136 Appendix B
1 1
d
d
N N
jk
jn nk jn nk
n n
p
i
p H H p
t
= =
 
= ÷

\ .
_ _
=
(B61)
Thedensitymatrix element d
jk
isnothingotherthantheproduct
p
jk
averagedoverthewholeensemble:
jk jk
d p =
On the other hand the Hamiltonian and its matrix elements are the
sameforallthesystemswithintheensemble, they arenotaffectedby
theoperationofaveraging.Takingtheaverageonbothsidesof(B61)
yields
1 1
d
d
N N
jk
jn nk jn nk
n n
d
i
d H H d
t
= =
 
= ÷
\ .
_ _
=

(B62)
According to the matrix multiplication rule (see Appendix A) the
sums in (B62)representmatrixelementsoftheproductsDHandHD,
so(B62)canbewrittenas
( ) ( ) ( )
d
d
jk jk jk
jk
D i i
D D D
t
 
(
= ÷ = ÷

¸ ¸
\ .
= =
H H H HD
This demonstrates (B41) since the time derivative of a matrix is
performedbytakingthederivativeofeachelement.
Angular Momentum and Rotation Operators 137
APPENDIX C: ANGULAR MOMENTUM
AND ROTATION OPERATORS
System (spin): A(1/2)
0 1 0
1
;
1 0 0 2 2
x y
i
I I
i
1
÷ (
= =
(
¸ ¸ ¸
(
(
¸
(C1)
1 0 0 1
1
;
0 1 0 0 2
z x y
I I iI
(
= +
(
÷
¸ ¸ ¸
(
=
(
¸
(C2)
cos sin cos sin
2 2 2 2
;
sin cos sin cos
2 2 2 2
x y
i
R R
i
o o
o o o o
o o o
(
(
= =
(
(
÷
(
¸ ¸ ¸
o
(
(
(
(
(
¸
(C3)
90 90
1 1
1 1
;
1 1
2 2
x y
i
R R
i
(
= =
(
÷
¸ ¸ ¸
1
1
(
(
¸
1
0
(
=
(
¸
(C4)
(C5)
180 180
0 0
;
0 1
x y
i
R R
i
(
=
(
÷
¸ ¸ ¸
System (spin): A(1)
0 1 0 0 0
1 1
1 0 1 ; 0
2 2
0 1 0 0 0
x y
i
I I i
i
÷ (
(
= =
(
(
¸ ¸ ¸
i
(
(
÷
(
(
¸
(C6)
1 0 0 0 1 0
0 0 0 ; 2 0 0 1
0 0 1 0 0 0
z x y
I I iI
(
(
= + =
(
( ÷
¸ ¸ ¸
(
(
(
(
¸
(C7)
138 Appendix C
cos 1 2 sin cos 1
1
2 sin 2cos 2 sin
2
cos 1 2 sin cos 1
x
i
R i i
i
o
o o o
o o
o o
(
o
o
+ ÷
(
= (
(
÷ +
(
¸ ¸
(C8)
1 cos 2 sin 1 cos
1
2 sin 2cos 2 sin
2
1 cos 2 sin 1 cos
y
R
o
o o o
o o o
o o o
(
+ ÷
(
= ÷ (
(
÷ ÷ +
(
¸ ¸
(C9)
90 90
1 2 1 1 2 1
1 1
2 0 2 ; 2 0 2
2 2
1 2 1 1 2 1
x y
i
R i i R
i
(
÷
(
= = ÷ (
(
÷ ÷
(
¸ ¸ ¸
(
(
(
(
(
¸
(
(
(C10)
(C11)
180 180
0 0 1 0 0 1
0 1 0 ; 0 1 0
1 0 0 1 0 1
x y
R R
÷ ( (
(
= ÷ = ÷
(
( ( ÷
¸ ¸ ¸ ¸
System (spin): A(1/2) X(1/2)
0 1 0 0 0 0 0
1 0 0 0 0 0 0
1 1
;
0 0 0 1 0 0 0 2 2
0 0 1 0 0 0 0
xA yA
i
i
I I
i
i
÷ (
(
(
= =
(
(
(
(
( ÷
(
¸ ¸ ¸
(
¸
(C12)
1 0 0 0 0 1 0 0
0 1 0 0 0 0 0 0
1
; ( )
0 0 1 0 0 0 0 1 2
0 0 0 1 0 0 0 0
zA x y A
I I iI
(
(
÷
(
= + =
(
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
(C13)
Angular Momentum and Rotation Operators 139
0 0 1 0 0 0 0
0 0 0 1 0 0 0
1 1
;
1 0 0 0 0 0 0 2 2
0 1 0 0 0 0 0
xX yX
i
i
I I
i
i
÷ (
(
÷
(
= =
(
(
¸ ¸ ¸
(
(
(
(
(
¸
(C14)
1 0 0 0 0 0 1 0
0 1 0 0 0 0 0 1
1
; ( )
0 0 1 0 0 0 0 0 2
0 0 0 1 0 0 0 0
zX x y X
I I i I
(
(
(
= + =
( ÷
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
(C15)
90 90
1 0 0 1 1 0 0
1 0 0 1 1 0 0
1 1
;
0 0 1 0 0 1 1
2 2
0 0 1 0 0 1 1
xA yA
i
i
R R
i
i
(
(
÷
(
= =
(
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
(
(
(
(
(
¸
(C16)
(C17)
180 180
0 0 0 0 1 0 0
0 0 0 1 0 0 0
;
0 0 0 0 0 0 1
0 0 0 0 0 1 0
xA yA
i
i
R R
i
i
(
(
÷
(
= =
(
(
÷
¸ ¸ ¸
90 90
1 0 0 1 0 1 0
0 1 0 0 1 0 1
1 1
;
0 1 0 1 0 1 0
2 2
0 0 1 0 1 0 1
xX yX
i
i
R R
i
i
(
(
(
= =
( ÷
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
(C18)
140 Appendix C
(C19)
180 180
0 0 0 0 0 1 0
0 0 0 0 0 0 1
;
0 0 0 1 0 0 0
0 0 0 0 1 0 0
xX yX
i
i
R R
i
i
(
(
(
= =
( ÷
(
÷
¸ ¸ ¸
(
(
(
(
(
¸
Examples of selectiverotationoperators,affectingonlyoneof
thetwopossibletransitionsofnucleusX:24or13.
90 (24) 90 (24)
0 2 0 0 0 2 0 0
0 1 0 0 1 0 1
1 1
;
2 2 0 2 0 0 2 0 0 0
0 0 1 0 1 0
x y
i
R R
i
(
(
(
= =
(
(
(
÷
¸ ¸ ¸
1
(
(
(
(
(
(
¸
(
(
(
(
(
¸
(C20)
(C21)
180 (24) 180 (24)
1 0 0 0 1 0 0 0
0 0 0 0 0 0 1
;
0 0 1 0 0 0 1 0
0 0 0 0 1 0 0
x y
i
R R
i
(
(
(
= =
(
(
÷
¸ ¸ ¸
13 13 90 ( ) 90 ( )
1 1 0 0 0
0 0 0 2 0 0 2 0
1 1
;
2 2 1 1 0 0 0
0 0 0 0 2 0 0
x y
i
R R
i
( (
( (
( (
= =
( (
÷
( (
( (
¸ ¸ ¸ ¸
1 0
1 0
2
(C22)
Angular Momentum and Rotation Operators 141
180 (13) 180 (13)
0 0 0 0 0 1 0
0 1 0 0 0 1 0 0
; (C23)
0 0 0 1 0 0 0
0 0 0 1 0 0 0 1
x y
i
R R
i
( (
( (
( (
= =
( ( ÷
( (
¸ ¸ ¸ ¸
SelectiverotationoperatorsforthenucleusA(transition12or34)
canbewritteninasimilarmanner.
System (spin): A(1) X(1/2)
Theenergystatesarelabeledaccordingtothefigurebelow.
A
A
A
A
X
X
X
E
E
E
E
E
E
1/2 1
1/2 1
1/2 1
1/2 0
1/2 1
1/2 0
1
2
3
4
5
6
0 0 1 0 0 0
0 0 0 1 0 0
1 0 0 0 1 0
1
(C24)
0 1 0 0 0 1
2
0 0 1 0 0 0
0 0 0 1 0 0
xA
I
(
(
(
(
=
(
(
(
(
(
¸ ¸
142 Appendix C
0 1 0 0 0 0
1 0 0 0 0 0
0 0 0 1 0 0
1
(C25)
0 0 1 0 0 0 2
0 0 0 0 0 1
0 0 0 0 1 0
xX
I
(
(
(
(
=
(
(
(
(
(
¸ ¸
I
y
can be written in the same way, taking (C6) and (C1) as starting
points.
ExamplesofrotationoperatorsfortheAX(1,1/2)system:
90
1 0 2 0 1 0
0 1 0 2 0 1
2 0 1 0 2 0
1
(C26)
2
0 2 0 1 0 2
1 0 2 0 1 0
0 1 0 2 0 1
yA
R
(
(
(
(
÷
(
=
(
÷
(
(
÷
(
(
÷
¸ ¸
180
0 0 0 0 0
0 0 0 0 0
0 0 0 0 0
(C27)
0 0 0 0 0
0 0 0 0 0
0 0 0 0 0
xX
i
i
i
R
i
i
i
(
(
(
(
=
(
(
(
(
(
¸ ¸
Reciprocals
1
R
÷
of all rotation operators can be found through
transpositionandcomplexconjugation(seeAppendixA).
Angular Momentum and Rotation Operators 143
Rotations about the zaxis
These rotation operators are needed in the following section
(Phase Cycling).Theycanbederivedinthesamewayasthexandy
rotationoperators[see(B45)to(B54)],afterobservingthat
 
1
forn=even
2
1
(2 ) forn=odd
2
n
z n
n
z z n
I
I I
 
=

\ .
 
=

\ .
1
(C28)
FortheonespinsystemA(1/2)wehave
0
0 *
z
b
R
b
o
(
=
(
¸ ¸
(C29)
with cos( / 2) sin( / 2) exp( / 2) b i i o o = + = o (C30)
ForthetwospinsystemA(1/2)X(1/2)wehave
(C31)
0 0 0 0 0 0
0 * 0 0 0 0 0
;
0 0 0 0 0 * 0
0 0 0 * 0 0 0 *
zA zX
b b
b b
R R
b b
b b
o o
( (
( (
( (
= =
( (
( (
¸ ¸ ¸ ¸
2
2
0 0 0
0 1 0 0
0 0 1 0
0 0 0 *
zAX zA zX
b
R R R
b
o o o
(
(
(
= =
(
(
(
¸ ¸
(C32)
144 Appendix C
Phase cycling
Thissectioncontainsrotationoperatorsforphase cycled pulses.
Therotationaxisforsuchpulsesissituatedinthexyplaneandmakes
an angle u with the xaxis. In succesive runs, the angle u assumes
different values. When u is equal to 0
o
, 90
o
, 180
o
, or 270
o
, the
rotationaxisisx, y, x ÷ ,or y ÷ ,respectively.Theexpressionsgiven
inthissectionarevalidfor any value of u,evenifitisnotamultiple
of90
o
. Such values areseldomusedinpulsesequencesbuttheymay
beusedtoassesstheeffectofimperfectphases.
The rotation operator R
90
represents a 90
o
rotation about an
axis making the angle u with the xaxis. In order to find the
expression of R
90
, we observe that this rotation is equivalent with
thefollowingsuccessionofrotations:
a.Arotationby ÷u(clockwise)aboutOz,bringingthe
rotationaxisinlinewithOx.
b.A90
o
rotationaboutOx.
c.Arotationby u(counterclockwise)aboutOz.
FortheonespinsystemA(1/2),using(C29),thisleadsto
90 ( ) 90 z x z
R R R R
u ÷u u
=
* 0 1 0
1
0 1 0
2
b i b
b i b
( ( (
=
( ( (
¸ ¸ ¸ ¸ ¸ ¸
*
2
2
* 0 * 1 * 1 1
0 * 1 2 2
b b ib ib
b ib b ib
( ( (
= =
( ( (
¸ ¸ ¸ ¸ ¸ ¸
(C33)
where from(C30).Withthenewnotation exp( / 2) b i = u
2
* exp( ) a ib i i = = ÷ u (C34)
therelation(C33)becomes
90
1
1
* 1
2
a
R
a
u
(
=
(
÷
¸ ¸
(C35)
Inasimilarwayonecandemonstratethat
Angular Momentum and Rotation Operators 145
180
0
* 0
a
R
a
u
(
=
(
÷
¸ ¸
(C36)
ForthetwospinsystemA(1/2)X(1/2)
90
1 0
* 1 0 0
1
0 0 1
2
0 0 * 1
A
a
a
R
a
a
u
0 (
(
÷
(
=
(
(
÷
¸ ¸
(C37)
90
1 0 0
0 1 0
1
* 0 1 0
2
0 * 0 1
X
a
a
R
a
a
u
(
(
(
=
( ÷
(
÷
¸ ¸
(C38)
2
90 90 90
2
1
* 1 1 1
2 * 1 1
* * * 1
AX A X
a a a
a a
R R R
a a
a a a
u u u
(
(
÷ ÷
(
= =
(
÷ ÷
(
÷ ÷ (
¸ ¸
(C39)
This operator has been used in the DM treatment of INADEQUATE
[see(I.83)].
Onecanverifythatfor u =0wehave a=iand
90 90 AX x AX
R R
u
= [cf.(I.34)]
When u=90
o
wehave a=1and
90 90 AX y AX
R R
u
= [cf.(I.101)]
146 Appendix C
Forthe180
o
pulse,similarcalculationsleadto
180
0 0
* 0 0 0
0 0 0
0 0 * 0
A
a
a
R
a
a
u
0 (
(
÷
(
=
(
(
÷
¸ ¸
(C40)
180
0 0 0
0 0 0
* 0 0 0
0 * 0 0
X
a
a
R
a
a
u
(
(
(
=
( ÷
(
÷
¸ ¸
(C41)
2
180
2
0 0 0
0 0 1 0
0 1 0 0
* 0 0 0
AX
a
R
a
u
(
(
÷
(
=
(
÷
(
(
¸ ¸
(C42)
The180
o
operatorscanbecalculatedbymultiplyingtherespective90
o
operatorwithitself(twosuccessive90
o
rotations).
Cyclops
Even in the simplestonedimensionalsequences,involvingone
single pulse (the "observe" pulse), a form of phase cycling is used in
order to eliminatetheradiofrequencyinterferences. Theobservepulse
is cycled through all four phases, e.g. clockwise: +x, ÷ y, ÷ x, +y.
The f.i.d. phase follows the same pattern. There will be no
accumulation unless the reciever phase is also cycled clockwise. An
extraneous signal is not phase cycled and it will be averaged out
becauseofthereceivercycling,providedthenumber of transients is a
multipleoffour.Theprocedureisknownas"cyclops".
Properties of Product Operators 147
APPENDIX D: PROPERTIES OF
PRODUCT OPERATORS
Asystemofmspin1/2nucleihasN=2
m
states.Thebasis set for
this system consists of N
2
product operators (PO) which are
hermitian matrices. Wesummarizeherethemostsignificantfeaturesof
thesematrices.
N N u
1. There is only one nonvanishing element per row. As a
consequence, any PO has only N nonvanishing elements out of N
2
elements.
2. There is also only one nonvanishing element per column.
Properties 1 and 2 are found in the matrices representing angular
momentum components I
x
, I
y
, I
z
(see Appendix C). A product of two
matriceshavingthesepropertiesinheritsthem.
3.ThenonvanishingelementsofaPOareeither 1 r or i r .
4. If P
j
and P
k
are two product operators from the basis set, the
trace(sumofdiagonalelements)oftheirproductis
Tr( )
j k jk
P P NG (D1)
where d
jk
(theKroneckerdelta)hasthevalue
d
jk
=0ifj z k
d
jk
=1ifj=k
The property (D1) illustrates the orthogonality of the PO's. The
product of two different PO's is traceless. The square of a given PO is
equaltotheunitmatrix,thereforeitstraceisequaltoN.
Expressing a given matrix in terms of PO's
Since the basis set is a complete set, any NuN matrix can be
expressedasalinearcombinationofPO's:
(D2)
2
1 1 2 2
... where
L L
D c P c P c P L N
148 Appendix D
Giventhematrix D,thecoefficientsc
j
canbedeterminedusingthe
orthogonalityrelation(D1).
(D3)
1 1
Tr( ) Tr( )
m m
j k k j k kj
k k
DP c P P c N Nc G
¦ ¦ j
Therefore
1
Tr( )
j
c D
N
j
P (D4)
In the PO treatment of NMR sequences we do not have to go
through the routine described above since we start with the density
matrix expressed in terms of PO's and we have rules for any rotation or
evolution which give the new density matrix also expressed in terms of
PO's. For the same reason, we do not need to know the PO's in their
matrixforminordertooperatewiththem.
Thecompletebasissetfor m=2(N=4)isgivenintableII.1.We
give in the following pages a few examples of PO's in matrix form for
m=3(N=8)andfor m=4(N=16).Attheendofthisappendixa
computer program can be found (written in BASIC) which can help
generatealltheproductoperatorsfor n=2,3,or4.
In all the matrices given below as examples, the dots represent
zeros.
1 . . . . . . .
. 1 . . . . . .
. . 1 . . . . .
. . . 1 . . . .
[111]
. . . . 1 . . .
. . . . . 1 . .
. . . . . . 1 .
. . . . . . . 1
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[11 ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
y
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
Properties of Product Operators 149
1 . . . . . . .
. 1 . . . . . .
. . 1 . . . . .
. . . 1 . . . .
[ 11]
. . . . 1 . . .
. . . . . 1 . .
. . . . . . 1 .
. . . . . . . 1
z
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[1 1]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
y
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . 1 .
. . . . . . . 1
. . . . 1 . . .
. . . . . 1 . .
[1 ]
. . 1 . . . . .
. . . 1 . . . .
1 . . . . . . .
. 1 . . . . . .
xx
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[ 1]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
xy
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[1 ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
xy
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[ ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
xyz
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[ ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
zxy
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[ 1 ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
x y
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
150 Appendix D
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[1 ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
zy
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[ ]
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
zzy
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . . 1
. . . . . . 1 .
. . . . . 1 . .
. . . . 1 . . .
[ ]
. . . 1 . . . .
. . . 1 . . . . .
. 1 . . . . . .
1 . . . . . . .
yxy
ª º
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« »
« »
« »
« »
« »
¬ ¼
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
[ ]
. . . . . . .
. . . . . . . .
. . . . . . .
. . . . . . .
i
i
i
i
yyy
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
¬ ¼
. 1 . . . . . . . . . . . . . .
1 . . . . . . . . . . . . . . .
. . . 1 . . . . . . . . . . . .
. . 1 . . . . . . . . . . . . .
. . . . . 1 . . . . . . . . . .
. . . . 1 . . . . . . . . . . .
. . . . . . . 1 . . . . . . . .
. . . . . . 1 . . . . . . . . .
[ 111]
. . . . . . . . . 1 . . . . . .
. . . . . . . . 1 . . . . . . .
. . . . . . . . . . . 1 . . . .
. . . . . . . . . . 1 . . . . .
.
x
. . . . . . . . . . . . 1 . .
. . . . . . . . . . . . 1 . . .
. . . . . . . . . . . . . . . 1
. . . . . . . . . . . . . . 1 .
ª º
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« »
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¬ ¼
Properties of Product Operators 151
. . . . . . 1 . . . . . . . . .
. . . . . . . 1 . . . . . . . .
. . . . 1 . . . . . . . . . . .
. . . . . 1 . . . . . . . . . .
. . 1 . . . . . . . . . . . . .
. . . 1 . . . . . . . . . . . .
1 . . . . . . . . . . . . . . .
. 1 . . . . . . . . . . . . . .
[1 1]
. . . . . . . . . . . . . . 1 .
. . . . . . . . . . . . . . . 1
. . . . . . . . . . . . 1 . . .
. . . . . . . . . . . . . 1 . .
.
xx
. . . . . . . . . 1 . . . . .
. . . . . . . . . . . 1 . . . .
. . . . . . . . 1 . . . . . . .
. . . . . . . . . 1 . . . . . .
ª º
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
[ 1]
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . .
i
i
i
i
i
i
i
i
xyz
i
i
i
i
. . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
¬ ¼
152 Appendix D
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
[ 1 ]
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . .
i
i
i
i
i
i
i
i
z yz
i
i
i
. . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
i
i
i
i
i
ª º
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
« »
¬ ¼
. . . . . . . . 1 . . . . . . .
. . . . . . . . . 1 . . . . . .
. . . . . . . . . . 1 . . . . .
. . . . . . . . . . . 1 . . . .
. . . . . . . . . . . . 1 . . .
. . . . . . . . . . . . . 1 . .
. . . . . . . . . . . . . . 1 .
. . . . . . . . . . . . . . . 1
[ ]
1 . . . . . . . . . . . . . . .
. 1 . . . . . . . . . . . . . .
. . 1 . . . . . . . . . . . . .
. . . 1 . . . . . . .
zzzx
. . . . .
. . . . 1 . . . . . . . . . . .
. . . . . 1 . . . . . . . . . .
. . . . . . 1 . . . . . . . . .
. . . . . . . 1 . . . . . . . .
ª º
« »
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¬ ¼
Alltheproductoperatorssampledinthis appendixhavebeencalculated
withtheprogramPOP(ProductOPerators)listedonthefollowingpages.
ItiswritteninBASIC,VersionCPM86,Rev.5.22byMicrosoft.
Properties of Product Operators 153
10REMPROGRAM"POP"CALCULATESANDPRINTSTHE
11REMBASICOPERATORSACCORDINGTOSORENSEN
12REMERNSTFORASYSTEMOFTWO,THREE,ORFOUR
13REMSPIN1/2NUCLEI
20DIMD%(256,16),N%(256,16),F%(256),J%(4),J$(4)
25DIMB$(256),A(16,16),B(16,16)
30PRINT"NUMBEROFSPIN1/2NUCLEI(2,3,OR4)"
40INPUTNN%
45IFNN%>4THENNN%=4
46IFNN%<2THENNN%=2
50REMNUMBEROFSTATES
60NS%=2^NN%
65IFNN%=2THENB$="14seconds"
66IFNN%=3THENB$="38seconds"
67IFNN%=4THENB$="2min46s"
68PRINT"Pleasewait";B$
70GOSUB940
71REMAllproductoperatorsarenowcalculatedandlabeled
75PRINT"MENU"
76PRINT"========="
78PRINT"ADisplayaspecifiedproductoperator"
80PRINT"BDisplayallproductoperators"
82PRINT"CPrintaspecifiedproductoperator(hardcopy)"
84PRINT"DPrintallproductoperators(hardcopy)"
86PRINT"EExpressamatrixintermsofproductoperators"
88PRINT"FSameasEbutprinted(hardcopy)"
118PRINT"XExitMENU"
120M%=14
125FORI%=1TOM%:PRINT:NEXTI%
130INPUTMENU$
135IFMENU$="A"THENGOSUB4050
137IFMENU$="B"THENGOSUB4000
139IFMENU$="C"THENGOSUB4050
141IFMENU$="D"THENGOSUB4000
143IFMENU$="E"THENGOSUB4500
145IFMENU$="F"THENGOSUB4500
170PRINT"DoyouwanttojointheMENUagain?(YorN)"
175INPUTA$
180IFA$="Y"THEN75
935END
940REMSubroutine9403650tocalculateallPOforgivenNN%
945REMZeroorderproductoperator(unitmatrix)
950FORM%=1TONS%
955N%(0,M%)=M%
960D%(O,M%)=1
965MEXTM%
970F%(0)=0
154 Appendix D
975REMFirstorderproductoperatorsIx,Iy,Iz
980FORK%=1TONN%
985K1%=2^(K%1):K2%=K1%*K1%
990F%(K2%)=0:F%(2*K2%)=1:F%(3*K2%)=0
995M%=1:SG%=1
1000FORC%=1TOK1%
1010N%(K2%,M%)=M%+SG%*K1%
1020N%(2*K2%,M%)=M%+SG%*K1%
1030N%(3*K2%,M%)=M%
1040D%(K2%,M%)=1
1050D%(2*K2,M%)=SG%
1060D%(3*K2%,M%)=SG%
1070M%=M%+1
1080NEXTC%
1090SG%=SG%
1100IFM%<=NS%THEN1000
1100NEXTK%
2000REMSecondorderbaseoperators(TwofactorPO's)
2010FORKA%=1TONN%1
2020FORKB%=KA%+1TONN%
2030FORJA%=1TO3
2040FORJB%=1TO4
2050K2A%=4^(KA%1)
2060K2B%=4^(KB%1)
2070SA%=JA%*K2A%:SB%=JB%*K2B%
2080GOSUB5000
2090NEXTJB%
2100NEXTJA%
2110NEXTKB%
2120NEXTKA%
3000REMThreefactorproductoperators
3010IFNN%<3THEN3625
3020FORKC%=1TONN%2
3030FORKD%=KC%+1TONN%1
3040FORKB%=KD%+1TONN%
3050FORJC%=1TO3
3060FORJD%=1TO3
3070FORJB%=1TO3
3080K2C%=4^(KC%1):K2D%=4^(KD%1):K2B%=4^(KB%1)
3090SC%=JC%*K2C%:SD%=JD%*K2D%:SB%=JB%*K2B%
3100SA%=SC%+SD%
3100GOSUB5000
3120NEXTJB%
3130NEXTJD%
3140NEXTJC%
3150NEXTKB%
3160NEXTKD%
Properties of Product Operators 155
3170NEXTKC%
3500REMFourfactorproductoperators
3510IFNN%<4THEN3625
3520FORJC%=1TO3
3530FORJD%=1TO3
3540FORJE%=1TO3
3550FORJB%=1TO
3560SA%=JC%+4*JD%+16*JE%
3570SB%=64*JB%
3580GOSUB5000
3590NEXTJB%
3600NEXTJE%
3610NEXTJD%
3620NEXTJC%
3625REMOperatorlabeling
3630FORS%=0TONS%^21
3635GOSUB3900
3637NEXTS%
3640REMAllproductoperatorsarenowcalculatedandlabeled
3641REMArraysd(s,m,),n(s,m),F(s)andB$(s)arefilled
3650RETURN
3900REMSubroutine39003045generateslabel,givens
3901B$="["
3904R%=S%
3908FORI%=1TONN%
3912J%(I%)=R%4*INT(R%/4)
3916R%=INT(R%/4)
3920IFJ%(I%)=0THENJ$(I%)="1"
3924IFJ%(I%)=1THENJ$(I%)="x"
3928IFJ%(I%)=2THENJ$(I%)="y"
3932IFJ%(I%)=3THENJ$(I%)="z"
3936B$=B$+J$(I%)
3940NEXTI%
3943B$=B$+"]"
3945RETURN
3950REMSubroutine39503995generatess,givenlabel
3952P=0:S%=0
3955FORI%=1TONN%
3960IFJ$(I%)="1"THENJ%(I%)=0GOTO3985
3965IFJ$(I%)="X"THENJ%(I%)=1GOTO3985
3970IFJ$(I%)="Y"THENJ%(I%)=2GOTO3985
3975IFJ$(I%)="Z"THENJ%(I%)=3GOTO3985
3980P=1:GOTO3995
3985S%=S%+4^(I%1)*J%(I%)
3990NEXTI%
3995RETURN
4000REMSubroutine40004040tooutputallproductoperators
156 Appendix D
4005IFMENU$="D"THENMENU$="C"
4010FORS%=0TONS%^21
4020GOSUB4155
4030NEXTS%
4040RETURN
4050REMSubroutine40504110tooutputonespecifiedPO
4051PRINT"Pleaselabeldesiredproductoperator,e.g.";
4052IFNN%=2THENB$="X,Yor1,Zetc."
4053IFNN%=3THENB$="X,Y,Zor1,X,Yetc."
4054IFNN%=4THENB$="X,Y,X,ZorX,Y,Z,1etc."
4055PRINTB$
4056PRINT"thenpressRETURN"
4060IFNN%=2THENINPUTJ$(1),J$(2)
4070IFNN%=3THENINPUTJ$(1),J$(2),J$(3)
4080IFNN%=4THENINPUTJ$(1),J$(2),J$(3),J$(4)
4090GOSUB3950
4095IFP>0THEN4105
4100GOSUB4155:GOTO4107
4105PRINT:PRINT:PRINT"Pleasetryagain"
4107PRINT"Doyouwantanother?(YorN)"
4108INPUTA$:IFA$="Y"THEN4050
4110RETURN
4155REMSubroutine41554275todisplayorprintonPO,givens
4160PRINT:PRINTB$(S%)+"=":PRINT
4166IFMENU$="C"THEN4167ELSE4170
4167LPRINT:LPRINTB$(S%)+"=":LPRINT
4170FORM%=1TONS%
4180FORI%=1TON%(S%,M%)1
4190PRINT".";
4195IFMENU$="C"THEN4196ELSE4200
4196LPRINT".";
4200NEXTI%
4210D%=D%(S%,M%)
4220GOSUB5300
4230PRINTD$;
4235IFMENU$="C"THEN4236ELSE4240
4236LPRINTD$;
4240FORI%=N%(S%,M%)=1TONS%
4250PRINT".";
4255IFMENU$="C"THEN4256ELSE4260
4256LPRINT".";
4260NEXTI%
4265PRINT
4266IFMENU$="C"THENLPRINTELSE4270
4270NEXTM%:PRINT:PRINT
4272IFMENU$="C"THEN4273ELSE4275
4273LPRINT:LPRINT
Properties of Product Operators 157
4275RETURN
4400PRINT"Doyouwantanother?(YorN)":INPUTH$
4410IFH$="Y"THEN4002
4500REMSubroutine45004790toexpressagivenmatrix
4501REMintermsofproductoperators
4530FORM%0TONS%:FORN%=0TONS%
4540A(M%,N%)=0:B(M%,N%)=0
4550NEXTN%:NEXTM%
4555PRINT"Howmanynonvanishingelementsinthematrix?"
4556INPUTN
4560PRINT"Foreverynonvanishingelementinyourmatrix"
4561PRINT"d(m,n)=a+i*b"
4562PRINT"pleaseenter:m,n,a,bthenpressRETURN"
4569FORI%=1TON
4570INPUTM%,N%,A,B
4580A(M%,N%)=A:B(M%,N%)=B
4590NEXTI%
4600T$="Yourmatrixhasthefollowingnonzeroelements"
4601PRINTT$
4601IFMENU$="F"THENLPRINTT$
4610FORM%=1TONS%:FORN%=1TONS%
4620IFA(M%,N%)=0THENIFB(M%,N%)=0THEN4640
4625B$="+i*":B=B(M%,N%)
4626IFB<0THENB=B:B$="i*"
4630PRINT"d("M%","N%")=",A(M%,N%),B$;B
4635IFNEMU$="F"THEN4636ELSE4640
4636LPRINT"d("M%","N%")=",A(M%,N%),B$;B
4640NEXTN%:NEXTM%
4645PRINT:PRINT:PRINT"Yourmatrix="
4646IFMENU$="F"THEN4647ELSE4650
4647LPRINT:LPRINT:LPRINT"Yourmatrix="
4650FORS%=0TONS%^21
4660R%=1F%(S%)
4665CR=0:CI=0
4670FORM%=1TONS%
4680N%=N%(S%,M%)
4690CR=CR+(A(M%,N%)*R%+B(M%,N%%)*F%(S%))*D%(S%,M%)
4700CI=CI+(B(M%,N%)*R%A(M%,N%%)*F%(S%))*D%(S%,M%)
4710NEXTM%
4720CR=CR/2:CI=CI/2
4730IFCR=0THENIFCI=0THEN4780
4735B$="+i":B=CI
4736IFCI<0THENB=B:B$="i*"
4740PRINT"("CR,B$;B;")*"B$(S$)
4745IFMENU$="F"THEN4746ELSE4780
4746LPRINT"("CR,B$;B;")*"B$(S$)
4780NEXTS%
158 Appendix D
4781PRINT:PRINT
4790RETURN
5000REMSubroutine50005090specialmatrixmultiplication
5010S%=SA%+SB%
5020FORM%=1TONS%
5030MB%=N%(SA%,M%)
5040N%(S%,M%)=N%(SB%,MB%)
5050D%(S%,M%)=D%(SA%,M%)*D%(SB%,MB%)5060NEXTM%
5070F%(S%)=F%(SA%)+F%(SB%)
5080IFF%(S%)>1THENGOSUB5100
5090RETURN
5100F%(S%)=0
5110FORM%=1TONS%
5120D%(S%,M%)=D%(S%,M%)
5122NEXTM%
5130RETURN
Demonstration of the Rotation Rules 159
APPENDIX E: DEMONSTRATION
OF THE ROTATION RULES
We demonstrate here the validity of the PO pulse rotations
derivedfromthevectorrepresentationin Section II.6 (correspondence
betweenthevectorrotationsandthePOformalism).
Demonstration of an ox rotation
Wewilldemonstrateanorotationaroundthexaxis:
cos sin
x
y y z
I I I
o
o o ÷÷÷ + (E1)
Other rotations can be demonstrated in asimilar way. We start from
the rotation operator applied to a density matrix and we make use of
thecommutationrulesfortheoperatorsI
x,
I
y,
I
z
,whichare:
x y y x z
I I I I iI ÷ =
y z z y x
I I I I iI ÷ = (E2)
z x x z y
I I I I iI ÷ =
It isnecessarytoemphasizethattheaboverulesapplynotonly
to an isolated spin but also to every particular nucleus in a multi
nuclear system (with or without coupling). In an AMX system for
instancewehavefornucleusA:
xA yA yA xA zA
I I I I iI ÷ = (andsoon)
Angular momentum components of different nuclei within a
systemarecommutative.Forinstance:
0
0
xA yM yM xA
xA xM xM xA
I I I I
I I I I
÷ =
÷ =
(E3)
TherotationoperatorR
ox
[see(B45)]hastheexpression:
exp( )
x x
R i I
o
o = (E4)
Appliedtoadensitymatrix D(n)itwillyield:
1
( 1) ( )
x
D n R D n R
x o o
÷
+ = (E5)
160 Appendix E
In(E1)wehaveassumedthatD(n)isequaltoI
y
,sowhatwe
havetodemonstrateis:
1
( 1) cos sin
x y x y x
D n R I R I I
o o
o o
÷
+ = = + (E6)
InAppendixBwehavedemonstrated[see(B51)]that
cos [ ] sin (2 )
2 2
x x
R i
o
I
o o
= + 1 (E7)
Introducingthisexpressionin(E6)gives
( 1) cos [ ] sin (2 ) cos [ ] sin (2 )
2 2 2 2
x y x
D n i I I i I
o o o o (
+ = ÷ +
(
¸ ¸ ¸
1 1
(
(
¸
2 2
cos 4sin 2 cos 4sin ( )
2 2 2 2
y x y x y x x y
I I I I i I I I I
o o o o
= + + ÷
Afterusingthefirstrelationin(E2)thisbecomes
2 2
( 1) cos 4sin 2 cos 4sin ( )
2 2 2 2
y x y x
D n I I I I i iI
z
o o o o
+ = + + ÷
2 2
cos 4sin sin
2 2
y x y x z
I I I I I
o o
o = + +
Ifweusenowtherelation
1
4
x y x y
I I I I = ÷
(E8)
whichwillbedemonstratedimmediately,weget
( 1) cos sin
y z
D n I I o o + = +
whichconfirms(E1).
To demonstrate (E8) we postmultiply the first relation in (E2)
by
x
I and,taking(B48)intoaccount,weobtain
1
4
x y x y z x
I I I I iI I ÷ =
(E9)
Premultiplyingofthefirstrelationin(E1)by I
x
yields
1
4
y x y x x z
I I I I iI I ÷ = (E10)
Demonstration of the Rotation Rules 161
Subtracting(E10)from(E9)gives
1
2 ( ) (
2
x y x y z x x z y y
) I I I I i I I I I i iI I ÷ = ÷ = = ÷
or
1
2
2
x y x y
I I I I = ÷
whichdemonstrates(E8).
Rotation operators applied to product operators
Suppose we have to apply the rotation operator the R
oxA
to the
product operator [yzy]. The latter is a shorthand notation for the
product.
(2 )(2 )(2 )
yA zM yX
I I I
The subscripts A, M, X refer to the different nuclei in the system.
Since these subscripts are omitted for simplicity in the product
operatorlabel[yzy],wehavetokeepinmindasaconventionthat the
different nuclei of the system appear in the product operators always
inthesameorder:A,M,X.
Whatwehavetocalculateis:
( 1) exp( ) 8 exp( )
xA yA zM yX xA
D n i I I I I i I o o + = ÷ (E11)
We have stated (E3) that I
xA
commutes with both I
zM
and I
yX
. This
enablesustorewrite(E11)as:
( 1) exp( ) exp( )8
xA yA xA zM yX
D n i I I i I I I o o + = ÷
andwehavereducedtheproblemtoaknownone.Using(E6)weget:
( 1) 8(cos sin )
yA zA zM yX
D n I I I I o o + = +
Inshorthandnotation:
[ ] [ ]cos [ }sin
xA
yzy yzy zzy
o
o o ÷÷÷÷ + (E12)
Thiscanbephrasedasfollows:Arotationoperatoraffects only
one factor in the product operator and leaves the others unchanged.
Theaffectedfactorparallelsthevectorrotationrules.
162 Appendix E
Thisistrueinthecaseofa selective pulse.Wehavesometimes
to handle nonselective pulses, affecting two or more nuclei in the
system.Insuchcases, the procedure tofollowistosubstitute(inthe
calculations, not in the hardware)thenonselectivepulsebyasequence
ofselectivepulsesfollowingimmediatelyoneafteranother.
Theproblem
[ ]
xMX
yzy
o
÷÷÷÷
hastobehandledas
[ ] [ ]cos [ ]sin
xM
yzy yzy yyy
o
o o ÷÷÷÷ ÷
2
[ ]cos [ ]cos sin
xX
yzy yzz
o
o o o ÷÷÷÷ +
2
[ ]sin cos [ ]sin yyy yyz o o ÷ ÷ o
]
(E13)
Thereadercaneasilycheckthat theorderinwhich oxMandoxXare
applied is immaterial. The procedure described above has to be
followed even if the spins affected by the pulse are magnetically
equivalent.
The result (E13) may seem unexpectedly complicated for one
single pulse. Fortunately, in most practical cases o is either 90
o
or
180
o
. In these cases, the procedure above leads to exhilariatingly
simpleresultslike:
90
[ ] [ ]
xMX
yzy yyz ÷÷÷÷÷
180
[ ] [ ]
xMX
yzy yzy ÷÷÷÷÷
90
[ ] [
xAM
xyz xzz ÷÷÷÷
Inthesecasesitisnotnecessarytosplitthenonselectivepulseinto
subsequentselectivepulses.
Demonstration of the Coupled Evolution Rules 163
APPENDIX F: DEMONSTRATION OF THE
COUPLED EVOLUTION RULES
Before going into the demonstration we need to point out two
limitations:
a.Itassumes I=1/2forallnucleiinthesystem
b.Itoperatesintheweakcouplingcase:
J(couplingconstant)<<Ao(chemicalshiftdifference)
Between r.f. pulses the evolution of a twospin system AX in
therotatingframeisgovernedbytheHamiltonian.
( ) 2
A zA X zX zA zX
I I JI I t = O + O + = H (F1)
Thedensitymatrix D(n+1)attheendoftheevolutionisrelatedtothe
initialmatrix D(n)as:
(F2) ( 1) exp( / ) ( ) exp( / ) D n i t D n i t + = ÷ = H = H
Since all terms in (F1) commute with each other, we can write the
evolutionoperatoras:
( ) ( ) ( ) ( ) exp / exp exp exp 2
A zA X zX zA zX
i t i tI i tI i JtI I t = O O = H
A X J
R R R =
where the order of the factors is immaterial. Relation (F2) can be
rewrittenas:
1 1 1
( 1) ( )
J X A A X J
D n R R R D n R R R
÷ ÷ ÷
+ = (F3)
In(F3)theactualcoupledevolutionisformallypresentedastheresult
ofthreeindependentevolutionsduetoshiftA,shiftX,and coupling J,
respectively. In fact this is the way the coupled evolutions are
handled inthePOformalism:asasuccessionofshiftevolutionsand
evolutionsduetospinspincoupling(couplingevolutions).
The shift evolutions (noncoupled evolutions) are actually z
rotations and are easily handled with the vector rotation rules.
Example:
[ ] [ ]cos [ ]sin
A
t
A A
xy xy t yy
O
÷÷÷÷ O + t O
X
[ ]cos cos [ ]cos sin
X
t
A X A
xy t t xx t
O
÷÷÷÷ O O ÷ O O t
X
[ ]sin cos [ ]sin sin
A X A
yy t t yx t t + O O ÷ O O
164 Appendix F
Or,withselfexplanatorynotations,
[ ] '[ ] '[ ] '[ ] '[ ]
A X
t t
xy cc xy cs xx sc yy
O O
÷÷÷÷÷÷÷÷ ÷ + ÷ ss yx (F4)
Theobjectofthisappendixistoderivetherulesforcalculating
1
( 1) ( )
J J
D n R D n R
÷
+ =
where
( ) exp 2
J zA zX
R i JtI I t = (F5)
and D(n) may be any of the product operators or a combination
thereof.
We have to find first an expression similar to (B51) for the
operator R
J
.Calculatingthepowersof I
zA
I
zX
wefind
( )
1
[ ]
4
n
zA zX n
I I = 1 forn=even (F6)
( )
1
4
4
n
zA zX zA zX n
I I I = I forn=odd (F7)
andthisleadsto
( cos [ ] sin 4
2 2
)
J zA zX
Jt Jt
R i I I
t t
= + 1 (F8)
anexpressionwecanuseincalculating
1
( 1) ( )
J J
D n R D n R
÷
+ = .
Itisnowthemomenttointroducespecific product operators for
D(n).Wehavetodiscussthreecases.
Case 1.BothnucleiAandXparticipatein the product operator
with zor1.Example:
( )( ) ( ) [ ] 2 2
zA zX
D n zz I I = =
InthiscaseD(n)commuteswithbothI
zA
andI
zX
andthisgives:
1 1
( 1) ( ) ( ) (
J J J J
D n R D n R D n R R D n
÷ ÷
+ = = = )
NoneofthePOs[zz],[z1],[1z],[11]isaffectedbythecoupling
evolution. As a matter of fact, all these POs have only diagonal
elementsandarenotaffectedbyanyevolution,shiftorcoupling.
Demonstration of the Coupled Evolution Rules 165
Case 2.BothnucleiAandXparticipateintheproductoperator
withanxoray.Example:
( )( )
( ) [ ] 2 2
xA yX
D n xy I I = =
We can demonstrate that this kind of product operator also is not
affectedbythecouplingevolution. Inordertodosowehavetotake
into account that, for I = 1/2, the components of the angular momen
tumaranticommutative:
x y y x
I I I I = ÷
y z z y
I I I I = ÷ (F9)
z x x z
I I I I = ÷
Thevalidityof(F9)canbeverifiedonthe expressions (C1, C2) of the
angular momentum components for I=1/2. Using (F8) to calculate
wehave ( 1 D n + )
( ) ( 1) cos [ ] sin 4 (4
2 2
zA zX xA yX
Jt Jt
D n i I I I I
t t (
+ = ÷ ×
(
¸ ¸
1 )
( ) cos [ ] sin 4
2 2
zA zX
J J
i I I
t t (
× +
(
¸ ¸
1
( ) ( )
2 2 3
cos 4 sin 4
2 2
xA yX zA zX xA yX zA zX
Jt Jt
I I I I I I I I
t t
= +
( )( )
2
cos sin 4
2 2
xA yX zA zX zA zX xA yX
Jt Jt
i I I I I I I I I
t t
+ ÷
Since the angular momentum componentsofAarecommutativewith
thoseofX[see(E3)],wecanrewritethelastresultas
( ) ( )
2 2 3
( 1) cos 4 sin 4
2 2
xA yX zA xA zA zX yX zX
Jt Jt
D n I I I I I I I I
t t
+ = +
( )( )
2
cos sin 4
2 2
xA zA yX zX zA xA zX yX
Jt Jt
i I I I I I I I I
t t
+ ÷ (F10)
Using (F9) we find out that the last parenthesis in (F10) is null. To
calculatetheproduct I
zA
I
xA
I
zA
I
zX
I
yX
I
zX
in(F10)weusethefollowing
166 Appendix F
relations,similarto(E8):
( ) / 4 ; ( ) / 4
zA xA zA xA zX yX zX yX
I I I I I I I I = ÷ = ÷
andwereduce(F10)to
( ) ( ) ( )
2 2
( 1) cos 4 sin 4 4 (
2 2
xA yX xA yX xA yX
Jt Jt
D n I I I I I I D n)
t t
+ = + = =
All POs inthesubset[xx],[yx],[xy],[yy]arenotaffectedbytheJevo
lution. Unlike the POs in Case 1, they are affected by the shift evo
lution (see F4). This is consistent with the fact that all the non
vanishing elementsofthesePOsaredoublequantumorzeroquantum
coherences. Thetransitionfrequenciescorrespondingtothesematrix
elementsdonotcontainthecouplingJ.
Case 3. The product operator exhibits z or 1 for one of the
nuclei and x or y for the other nucleus. Only this kind of product
operatorisaffectedbythecoupling.Example:
( ) [ 1] 2
xA
D n x I = =
CalculationssimilartothoseperformedinCase2leadto:
( ) ( ( 1) cos [ ] sin 4 2
2 2
zA zX xA
Jt Jt
D n i I I I
t t (
+ = ÷ ×
(
¸ ¸
1 )
( ) cos [ ] sin 4
2 2
zA zX
Jt Jt
i I I
t t (
× +
(
¸ ¸
1
( ) ( )
2 2
cos 2 sin 32
2 2
xA zA zX xA zA zX
Jt Jt
I I I I I I
t t
= +
( ) cos sin 8 8
2 2
xA zA zX zA zX xA
Jt Jt
i I I I I I I
t t
+ ÷
( ) ( )
2 2
cos 2 sin 32
2 2
xA zA xA zA zX
Jt Jt
2
I I I I I
t t
= +
( ) cos sin 8 8
2 2
xA zA zX zA xA zX
Jt Jt
i I I I I I I
t t
+ ÷
Demonstration of the Coupled Evolution Rules 167
( ) ( )
2 2
cos 2 sin 2
2 2
xA xA
Jt Jt
I I
t t
= ÷
( ) cos sin 8
2 2
xA zA zA xA zX
Jt Jt
i I I I I ( ) I
t t
+ ÷
( ) ( )
2 2
cos 2 sin 2
2 2
xA xA
Jt Jt
I I
t t
= ÷
( )( ) cos sin 8
2 2
yA zX
Jt Jt
i iI I
t t
+ ÷
cos (2 ) sin (4 )
xA yA zX
Jt I Jt I I t t = +
cos [ 1] sin [ ] Jt x Jt yz t t = +
Wehavedemonstratedthat
[ 1] [ 1]cos [ ]sin
J coupl
x x Jt yz Jt t t ÷÷÷÷ +
AfterdoingsimilarcalculationsforallthePOsin this category
(i.e., [x1],[1x],[y1],[1y],[xz],[zx],[yz],[zy]), we can summarize the
followingrulesfortheevolutionduetothecoupling J :
AX
a. ThecouplingevolutionoperatorR
J
affectsonlythoseproduct
operatorsinwhichoneof thenucleiA,Xisrepresentedby x or y while
theotherisrepresentedby1orz.
b. The effect of the J evolution is a rotation of x (or y) in the
equatorialplaneby tJt,whilezisreplacedby1and1by zinthenew
term.Theformatis:
POafter Jevolution=costJt(formerPO)+sintJt(formerPO
inwhichxisreplacedby y, ybyx, zby1and1by z).Insystems
withmorethantwonuclei,everynonvanishingcouplinglike J
AM
, J
AX
,
J
MX
, etc., has to be taken into account separately (the order is
immaterial).
Note 1. From Appendices E and F it results that any rotation
(r.f. pulse) or coupled evolution turns a given PO into a linear
combinationofPOswithinthebasisset. In otherwords,ifthedensity
matrix can beexpressedintermsofPOsatthestartofasequencewe
will be able to express it asacombinationofPOsatanypointofthe
sequence.ThisconfirmsthatthePObasissetisacompleteset.
Note 2.Moreover,inacoupledevolution,any xoryinthe
168 Appendix F
product operator can only become an x or y. Any z or 1 can only
becomeazor1.Thisleadstoanaturalseparationofthebasisset
(N
2
productoperators)intoNsubsetsofNoperatorseach.
InthecaseofN=4(twonuclei)thefoursubsetsare:
1)[11],[1z],[z1],[zz]
2)[x1],[y1],[xz],[yz]
3)[1x],[zx],[1y],[zy]
4)[xx],[yx],[xy],[yy]
InthecaseofN=8(threenuclei)theeightsubsetsare:
1)[111],[z11],[1z1],[zz1],[11z],[z1z],[1zz],[zzz]
2)[x11],[y11],[xz1],[yz1],[x1z],[y1z],[xzz],[yzz]
3)[1x1],[zx1],[1y1],[zy1],[1xz],[zxz],[1yz],[zyz]
4)[xx1],[yx1],[xy1],[yy1],[xxz],[yxz],[xyz],[yyz]
5)[11x],[z1x],[1zx],[zzx],[11y],[z1y],[1zy],[zzy]
6)[x1x],[y1x],[xzx],[yzx],[x1y],[y1y],[xzy],[yzy]
7)[1xx],[zxx],[1yx],[zyx],[1xy],[zxy],[1yy],[zyy]
8)[xxx],[yxx],[xyx],[yyx],[xxy],[yxy],[xyy],[yyy]
Underacoupledevolution,thedescendentsofaPOaretobe
foundonlywithinitsownsubset.
PO Evolution Tables 169
APPENDIX G: PO EVOLUTION TABLES
The tables below summarize the effect of a coupled evolution
oneachofthesixteenPOsofanAXsystem(twospin1/2nuclei).The
firstcolumnineachtableindicatesthePObeforetheevolution,while
thenextcolumnsindicatethenewlycreatedPOs(includingtheinitial
one). A coupled evolutionimpliesthreePOoperations:shiftA,shift
X, coupling J. Nevertheles no more than four terms are generated
fromtheinitialone:whenbothshiftsareactivethecouplingisnot.
a.Firstsubset(notaffectedbyevolution)
InitialPO FinalPOs
[11] [11] 0 0 0
[ ] z1 0 [ ] z1 0 0
[ ] 1z 0 0 [ ] 1z 0
[ ] zz 0 0 0 [ ] zz
b.Secondsubset(affectedbyAshiftandJcoupling)
InitialPO FinalPOs
[ ] x1 cC x [ ] 1 sC y [ ] 1 sS xz [ ] cS yz [ ]
[ ] y1 sC x [ ] 1 cC y [ ] 1 cS xz [ ] sS yz [ ]
[ ] xz sS x [ ] 1 cS y [ ] 1 cC xz [ ] sC yz [ ]
[ ] yz cS x [ ] 1 sS y [ ] 1 sC xz [ ] cC yz [ ]
170 Appendix G
c.Thirdsubset(affectedbyXshiftandJcoupling)
InitialPO FinalPOs
[ ] 1x c C x ' [ ] 1 s S zx ' [ ] s C y ' [ ] 1 c S zy ' [ ]
[ ] zx s S x ' [ ] 1 c C zx ' [ ] c S y ' [ ] 1 s C zy ' [ ]
[ ] 1y
s C x ' [ ] 1 c S zx ' [ ]
c C y ' [ ] 1 s S zy ' [ ]
[ ] zy
c S x ' [ ] 1 s C zx ' [ ]
s S y ' [ ] 1 c C zy ' [ ]
d.Fourthsubset(affectedbyAshiftandXshift)
InitialPO FinalPOs
[ ] xx cc xx '[ ] sc yx '[ ] cs xy ' [ ] ss yy ' [ ]
[ ] yx sc xx '[ ] cc yx '[ ] ss xy ' [ ] cs yy ' [ ]
[ ] xy cs xx '[ ] ss yx '[ ] cc xy '[ ] sc yy '[ ]
[ ] yy ss xx ' [ ] cs yx '[ ] sc xy '[ ] cc yy '[ ]
cos ; ' cos ; cos
sin ; ' sin ; sin
A X
A X
c t c t C
s t s t S
Jt
Jt
S
S
: :
: :
Demonstration of the Refocusing Rules 171
APPENDIX H: DEMONSTRATION
OF THE REFOCUSING RULES
We demonstrate here the validity of the rules stated in Section
II.8tohandlearefocusingroutine:
' '
180
When handling this segment of a sequence in the conventional
waywehavetosubjectthedensitymatrix D(n)toastringofoperators
representing the A/2 evolution (shifts and couplings), the r.f. pulse
(R
180
), then again the A/2 evolution. For two nuclei the string would
be:
180 A X AX AX X A
R R R R R R R R = (H1)
where R
A
, R
X
areshiftoperatorsandR
AX
isthecouplingoperator.
All shift and coupling evolution operators commute with each
other. In order to simplify the expression (H1) we have to find out
howtheycommutewithR
180
.Letusconcentrateononenucleus(e.g.,
nucleus A) and see how R
A
commutes with R
180xA
. According to
relation(B51)
180
exp( ) cos [ ] sin (2 ) 2
2 2
xA xA xA xA
R i I i I iI
t t
t = = + = 1 (H2)
AsimilarexpressioncanbewrittenfortheshiftevolutionoperatorR
A
whichrepresentsarotationby o = O
A
A /2aroundthezaxis.
exp( ) cos [ ] sin (2 )
2 2
A A zA zA
R R i I i
o
I
o o
o = = = + 1 (H3)
172 Appendix H
Wewanttoexaminetheproductofthetwooperators:
180
2 cos [ ] sin (2
2 2
xA A xA zA
R R iI i I
o
o o
)
(
= +
(
¸ ¸
1
Usingtheanticommutativityof I
x
andI
z
for I=1/2statedin(F10)we
canrewritetheproductas
180 ( ) 180
cos [ ] sin (2 ) 2
2 2
xA A zA xA A xA
R R i I iI R R
o o
o o
÷
(
= ÷ =
(
¸ ¸
1
We notice that R
(D)A
is the reciprocal of R
DA
since their combined
action would leave the density matrix unaffected. We can therefore
write
(H4)
1
180 180 xA A A xA
R R R R
o o
÷
=
andthisisthecommutationruleweneeded.
Onecancheckthattheruleisthesameifinsteadof R
180xA
we
use R
180yA
or R
180)A
(180
o
rotation about an arbitrary axis in the xy
plane).Forthelastcaseonehasuse
2
180 ( ) 180 180 180 (2 ) A zA xA zA A zA xA
R R R R R R R R
u ÷u u u u u
= = =
zA
u
( ) 2 cos [ ] sin 2 cos 2 sin ( 2 )
xA zA xA yA
iI i I iI i iI = u + u = u + u ÷ 1
180 180
cos sin
xA yA
R R = u+
Wehaveusedhere / 2
xA zA yA
I I iI = ÷ whichisaconsequenceof(E2)
and(F9).
Thereforewecanwriteingeneral
(H5)
1
180 180 A A A xA
R R R R
÷
=
Ontheotherhandwehave
180 180 A X X xA
R R R R = (H6)
sinceoperatorsactingondifferentnucleialwayscommute.
Asimilarpatterncanbefollowedtodemonstrate
Demonstration of the Refocusing Rules 173
(H7)
1
180 180 A AX AX A
R R R R
÷
=
(H8)
1
180 180 X AX AX X
R R R R
÷
=
With these commutation rules we now can rearrange astring like the
onein(H1):
1 1
180 180 A X AX A AX X A A X AX AX X A A
R R R R R R R R R R R R R R R
÷ ÷
= =
2 2
180 180 X A A X
R R R R = =
Only the shift X is expressed in the final result, while shift A and
couplingAXarerefocused.SinceR
X
istheshiftevolutionforA/2,
2
X
R
istheoperatorforthefulldelay A.
If the 180
o
pulse is applied on both nuclei A and X, the
rearrangingyields:
1 1
180 180 180 180 A X AX A X AX X A A X AX A AX X A X
R R R R R R R R R R R R R R R R R
÷ ÷
= =
1 1 2 2
180 180 180 180 180 180 A X AX AX X A A X AX A X A X AX
R R R R R R R R R R R R R R
÷ ÷
= = =
Both shifts are refocused, the coupling only is expressed in the final
result.ThisconfirmstherefocusingrulesstatedinSectionII.8.There
isnodifficultyinextendingthemtomorethantwonuclei.
174 Appendix I
APPENDIX I: SUPPLEMENTARY DISCUSSIONS
2DHETCOR without A
1
ItisstatedinPartI,Section3.7,thatinorder to understand the
role of the delay A
1
(see Figure I.2) we should carry on the
calculationswithoutit.Wedothishere.
We start by writing the density matrix before the combined
90xCHpulse:
3 0 0
0 2 0
(5) (I1)
* 0 3 0
0 * 0 2
F
G
D
F
G
(
(
(
=
(
(
¸ ¸
Ifwehavethedelay A
1
=1/2J,theexpressionsforFandG are taken
from(I.32):
13 1
24
(5) 2exp[ ( )]
(5)
H e
F d i t
G d F
= = ÷ ÷ O + A
= = ÷
(I2)
If A
1
is not used, the expressions for F and G, taken from (I.25) and
(I.26),are:
(I3)
13
(4) 2 exp( )
H e
F d i i t G = = ÷ ÷ O =
WeapplytheoperatorR
90xCH
givenin(I.34)toD(5)in(I1).
90
3 3 3 3
2 2 2 2
1
(5)
3 * 3 * 3 * 3 * 2
2 * 2 * 2 * 2 *
xCH
iF i F i F iF
i G iG iG i G
D R
i F iF iF i F
iG i G i G iG
+ ÷ + ÷ + (
(
÷ + ÷ + +
(
=
( + ÷ + + ÷
(
÷ + + ÷ +
¸ ¸
Supplementary Discussions 175
Premultiplicationwith
1
90xCH
R
÷
givesthefollowingexpressionforD(7)
10 ( 2 (
* *) * * * * * *)
2 10 ( (
* * * *) * *) * *
1
4
( 10 ( 2
* * * *) * *) * *
( 2 1
* *) * * * * * *)
i F G i F G F G i F G
F G F G F G F G
i F G i F G i F G F G
F G F G F G F G
F G i F G i F G i F G
F G F G F G F G
i F G F G i F G i F G
F G F G F G F G
+ + ÷ + + ÷
÷ ÷ + ÷ + + + ÷
÷ + ÷ + + ÷ ÷ +
÷ + ÷ ÷ + ÷ + +
+ ÷ ÷ + +
+ + + ÷ ÷ ÷ ÷ +
÷ ÷ + ÷ ÷ + ÷ +
+ ÷ + + + ÷ ÷ ÷
¸
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
¸
0 (
÷
(I4)
Now we can see why having G = F is counterproductive. The
factors F and G contain the proton information [see (I3)] and, when
they are equal, thisinformationdisappearsfromtheobservablesingle
quantumcoherencesd
12
andd
34
.InthiscaseD(7)becomes
5 * 2 * 0
2 5 * 0 *
1
(7)
* 0 5 * 2 2
0 * 2 5
iF iF i F F
i iF iF F F
D
F F iF iF i
F F i iF iF
+ ÷ + (
(
÷ + ÷ +
(
=
( + ÷ ÷
(
+ ÷ ÷ ÷
¸ ¸
*
(I5)
176 Appendix I
No pulse follows after t(7) and each matrix element evolves in
its own"slot."Thematrixelements d
12
andd
34
.willbeaffectedbythe
carbon evolution during the detection t
d
(preceded or not by the
coupledevolutionA
2
) buttheywillnotbeprotonmodulated.Wewill
nothavea2D.
TheDMcalculationsinSections3.6to3.9havebeen carried on
withthedelay A
1
= 1/2J,i.e,withG= ÷ F[see(I2)].InthiscaseD(7)
is
5 * 0 (
* 5 ( *) 0
1
(7)
0 ( *) 5 2
( *) * * 5
i F F i F F
i F F i F F
D
i F F i F F
i F F F F i F F
÷ + + (
(
÷ + ÷ ÷ +
(
=
( + +
(
÷ + + ÷ ÷ +
¸ ¸
*)
* ÷
(I6)
Taking Ffrom(I2)andusingthenotations(I.31)
1
1
cos[ ( )]
sin[ ( )]
H e
H e
c t
s t
= O + A
= O + A
weobtain
2( )
* 4
* 4
F c i
F F is
F F c
s = ÷ ÷
÷ =
+ = ÷
(I7)
By introducing (I7) into (I6) we can verify the expression of D(7)
given in (I.35). The carbon observables d
12
and d
34
contain now the
factor s which carries the proton information. The role of the
subsequentcoupledevolution'
2
isexplainedinSection3.9.
Supplementary Discussions 177
2DHETCOR without the 180xC pulse
We demonstrate here the result (I.51). The density matrix at
t(1),takenfrom(I.12),is
2 0 2 0
0 3 0 2
(1) (I8)
2 0 2 0
0 2 0 3
i
i
D
i
i
÷ (
(
÷
(
=
(
(
¸ ¸
Since the 180xC pulse and the delay A
1
are suppressed, all we have
between t(1)andt(5)isanevolutiont
e
.Thedensitymatrixjustbefore
the90xCHpulseisthen
2 0 0
0 3 0
(5) (I9)
* 0 2 0
0 * 0 3
B
C
D
B
C
(
(
(
=
(
(
¸ ¸
with
13
24
2 exp( )
2 exp( )
e
e
B i i t
C i i t
= ÷ ÷ O
= ÷ ÷ O
(I10)
Weapplythe180xCHoperatorto(I9).
90
2 2 2 2
3 3 3 3
1
(5)
2 * 2 * 2 * 2 * 2
3 * 3 * 3 * 3 *
xCH
iB i B i B iB
i C iC iC i C
D R
i B iB iB i B
iC i C i C iC
+ ÷ + ÷ + (
(
÷ + ÷ + +
(
=
( + ÷ + + ÷
(
÷ + + ÷ +
¸ ¸
178 Appendix I
Premultiplicationwith
1
90xCH
R
÷
givesthefollowingexpressionforD(7)
10 ( 2 (
* *) * * * * * *)
2 10 ( (
* * * *) * *) * *
1
4
( 10 ( 2
* * * *) * *) * *
( 2 1
* *) * * * * * *)
i B C i B C B C i B C
B C B C B C B C
i B C i B C i B C B C
B C F C B C B C
B C i B C i B C i B C
B C B C B C B C
i B C B C i B C i B C
B C B C B C B C
+ + ÷ + + ÷
÷ ÷ + ÷ + + + ÷
÷ + ÷ + + ÷ ÷ +
÷ + ÷ ÷ + ÷ + +
+ ÷ ÷ + + ÷
+ + + ÷ ÷ ÷ ÷ +
÷ ÷ + ÷ ÷ + ÷ +
+ ÷ + + + ÷ ÷ ÷
¸
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
¸
0 (
(I11)
We follow now the evolution of the carbon singlequantum
coherences.
12
1
(7) ( 2 * *)
4
d i B C B = ÷ ÷ + + ÷C
34
1
(7) ( 2 * *)
4
d i B C B = ÷ + ÷ ÷ +C
i
12 34
(7) (7) d d + = ÷
(I12)
The terms B and C, which contain the proton information, are absent
from the sum. If we start the acquisition at t(7), with the decoupler
on,wewillnothavea2D.Thisiswhy A
2
stillisnecessary.
Proceedingasin(I.36)to(I.43)wehave:
12 12 2 2
12 2
34 34 2
(8) (7) exp( ) exp( )
(7) exp( ) (I13)
(8) (7) exp( )
C
C
C
d d i i J
id i
d id i
t = ÷ O A ÷ A
= ÷ ÷ O A
= + ÷ O A
Supplementary Discussions 179
Treatingthedetectionasin(I.44)to(I.47)weobtain
(I14)
12 12 2
34 12 2
(9) (7) exp( ) exp( )
(9) (7) exp( ) exp( )
C
C C
d id i i t
d id i i t
= ÷ ÷ O A ÷ O
= + ÷ O A ÷ O
C d
d
( ) ( )
* *
12 34
(9) 9 9
TC oC
M M d d ( = +
¸ ¸
( ) ( )
* *
12 34 2
7 7 exp( ) exp( )
oC C C d
iM d d i i t ( = ÷ ÷ O A O
¸ ¸
 
2
( / 2)( * *) exp (
oC C d
i M B B C C i t = ÷ ÷ ÷ + O + A ) (I15)
From(I10)wehave
( ) ( )
13 13 13 13
* 2 cos sin 2 cos sin
e e e e
B B i t i t i t i t ÷ = ÷ O ÷ O ÷ O + O
(I16)
13
4 cos
e
i = ÷ O t
24
* 4 cos
e
C C i t ÷ = ÷ O (I17)
 
13 24 2
(9) ( / 2)( 4 cos 4 cos ) exp ( )
TC oC e e C d
M i M i t i t i t = ÷ ÷ O + O O + A
 
13 24 2
2 (cos cos ) exp ( )
oC e e C d
M t t i t = ÷ O ÷ O O + A
whichconfirms(I.51).
Fully coupled 2DHETCOR
Iftheprotondecouplerisnotturnedonduringthedetection, the
matrix elements d
12
and d
34
,will evolve with different frequencies in
thedomain t
d
.Eachofthemisprotonmodulated,eveniftheirsumat
time t(7) is not, and this renders the delay A
2
unnecessary. The
detectionstartsatt(7)andwewillhave
( ) ( )
* *
12 12 34 34
(9) 7 exp( ) 7 exp( )
TC oC d d
M M d i t d i t ( = ÷ O + O
¸ ¸
By introducing (I12), (I16), and (I17) in the expression above we
obtain
( )
( )
13 24 12
13 24 34
(9) 1 2 cos cos exp( )
1 2 cos cos exp( )
TC oC e e d
oC e e d
M iM t t i t
iM t t i t
= ÷ ÷ O + O O
÷ + O ÷ O O
whichconfirms(I.52).
180 Appendix J
APPENDIX J: PRODUCT OPERATORS AND
MAGNETIZATION COMPONENTS
Finding the magnetization components
Suppose that at a given moment t(n) of the sequence we have
thedensitymatrix D(n)expressedintermsofproductoperators.The
xmagnetizationcomponentsfornucleiA,M,X(wetakeathreespin
systemasanexample)aregivenby:
( ) ( / ' ) coefficientof[ 11]in ( )
xA oA A
M n M p x D n
( ) ( / ' ) "[1 1]" ( )
xM oM M
M n M p x D n (J1)
( ) ( / ' ) "[11 ]" ( )
xX oX X
M n M p x D n
withsimilarexpressionsforM
y
andM
z
.
M
oA
, M
oM
, M
oX
are the equilibrium magnetizations for the
respectivenuclei.Thefactorp' is relatedtotheBoltzmannfactorand
hastheexpression
' / 2 / 2
A A A
p p N NkT : = (J2)
withsimilarexpressionsfor ' , '
M X
p p (fortwonucleiweadoptp, q
insteadofp
A
, p
X
). N = total numberofquantumstatesinthesystem
(degenerateornot).FormnucleiwithI=1/2wehaveN=2
m
.
Thequantity1/N representstheaveragepopulationperstateas
the total population is normalized to l. The above procedure is
justified by the relation (B17), keeping in mind the orthogonality of
productoperators(relationD1).
Fast and slow magnetization components
In the first part of this book, when deriving the magnetization
components from the density matrixelements,wefounditinstructive
tocalculateseparatelythefastandslowcomponentsofthetransverse
magnetization(seeSectionI.3.9).ThiscanbeachievedinthePOfor
malismaswell.
Product Operators and Magnetization Components 181
For an AX system (two spin 1/2 nuclei), one can split the M
xA
magnetizationintoM
x12
(fast)andM
x34
(slow)asfollows:
12
coeff.of[ 1]+coeff.of[ ]
2 '
oA
x
M
M x x
p
z
34
coeff.of[ 1] coeff.of[ ]
2 '
oA
x
M
M x x
p
z
withsimilarrelationsforM
y
.
FornucleusXthefastandslowcomponentsare:
13
coeff.of[1 ]+coeff.of[ ]
2 '
oA
x
M
M x z
p
x
24
coeff.of [1 ] coeff.of[ ]
2 '
oA
x
M
M x z
p
x
UsingTableII.1,onecancheckthat
[1 ] [ ] 2 x zx and [1 ] [ ] 2 x zx
representthematrixelements d
13
andd
24
,respectively.
Writing the initial density matrix
We assume usually that, before the pulse sequence starts, all
spinsareatthermalequilibriumwiththelattice.
With the sign convention adopted in this book (vide infra) the
densitymatrix D(0)willbe:
(J3) (0) ' [ 11] ' [1 1] ' [11 ]
A M X
D p z p z p z
0
z
Thisisconsistentwith
o
; 0 ;
zA A xA yA
M M M M
andisthesameforspinsMandX.
Ifweworkinasteadystateinwhich one of the nuclei (let's say
nucleus A) does not have enough time to recover from the previous
cycle,wecanstartwith
(0) ' [ 11] ' [1 1] ' [11 ]
A M X
D p z p z p O (J4)
182 Appendix J
where 1 O d .IfM
zA
hasbeenbroughttozerobythelastpulseofthe
sequenceandthestartofthenextsequencecomesafteradelay d,then
1
1 exp /
A
d T O
Generally we start a sequence with no transverse magnetization; this
impliesthatdislongenoughwithrespecttoT
2
forallnuclei.
Sign convention
Throughout this book the conventional positive sense (right
hand rule) has been adopted for all rotations (due to pulses or
evolutions). For instance a rotation about Oz brings the magnetiza
tionfrom xtoy,to x,to y.ArotationaboutOxgoes:
y to zto y to z
This is the actualsenseofprecessionwhenthemagnetogyricratio,J
is negative. It has been assumed that the main magnetic field B
o
is
directed upwards (along +Oz) and thus at equilibrium the
magnetization is directed up and the angular momentum is directed
downwards(along Oz)whichisalsoconsistentwithanegativeJ.
This way, the most populated state is the one with the angular
momentum negative.MostfeaturesoftheNMRsequences(oneand
twodimensional) do not depend on the sign of J for all practical
purposes. Commercial NMR spectrometers do not provide specific
means to distinguish the sign of J. Therefore the above rules can be
applied for all nuclei in the system, no matter what the sign of their
magnetogyricratio.
IfforspecialpurposesthesignofJ has tobetakenintoaccount,
thenforpositiveJwehavetouselefthandrotationrules and start at
thermalequilibriumwithI
z
directedupwards.
When to Drop NonObservable Terms 183
APPENDIX K: WHEN TO DROP
NONOBSERVABLE TERMS (NOT)
In the expression of the density matrix we are interested in
thosePOswhichrepresentobservablemagnetization components: M
x
and M
y
for thenucleus(ornuclei)whichareobserved(seeAppendix
J). Wehavetocarryallthenonobservabletermsthroughthecalcula
tions as long as there is a possibility for them to generate observable
terms(followingapulseoranevolution).
It is useful to be aware when it is safe to drop the non
observable terms, or just include them in the nondescript designation
NOT.
Rule #1.InthefinalexpressionD(n)ofthedensitymatrix we
have to write down explicitly the observable terms only for the spe
cificnucleuswhichisobserved.ThisincludesthePOswhichshowx
or yfortheobservednucleusand1forallothers.
Rule #2. A decoupled evolution does not generate observable
POs out ofNOTorthereverse:itmerelyreplacesxby yoryby x.
So, if the last event of the sequence (the detection) is a decoupled
evolution,wecandotheselectionearlier,whenwritingD(n 1).
Rule #3. Acoupledevolutioncaninterchangexandybutalso
1 and z. Although, we can do some term dropping before the last
evolution,evenifcoupled. In writing D(n 1)wewillretainonlythe
POswhichcontainxoryforthenucleustobeobservedandz or1for
theothernuclei.EverythingelseisaNOT.
Forinstance,ifweobservenucleusA(in an AMX system), the
followingtermsmustbekept:
[x11],[x1z],[xz1],[xzz],[y11],[y1z],[yz1],[yzz].
Note.Ifapulsestillfollows,itis recommended to use utmost
careindroppingterms.Anexperiencedstudent will find for example
that if the observable is A and the last pulse is on X, terms like [1x],
[1z],[zx],(noxoryinpositionA)canbelabeledasNOTbeforethe
pulsesinceanXpulsewillneverrenderthemobservable.
184 Appendix L
APPENDIX L: MAGNETIC EQUIVALENCE,
THE MULTIPLET FORMALISM
While the PO formalism is basically a shorthand notation for
densitymatrixcalculations,weintroducehereanevenmore compact
notation (we call it the the multiplet formalism) to simplify the PO
treatment of CH
n
systems. In such a system n nuclei out of n+1 are
magneticallyequivalent.
ThedensitymatrixatthermalequilibriumforaCH
3
systemis:
D(0)= ÷ p'[z111] ÷ q'([1z11]+[11z1]+[111z]) (L1)
Weintroducethenotation{1z}forthesuminparenthesesandwrite
D(0)as:
D(0)= ÷ p'[z111] ÷ q'{1z} (L2)
Thenotation{1z}isnotonlyshorterbutitallows us to write the last
sumwithoutspecifyingthenumberofprotons in the system CH
n
.We
maketheconventionthat:
{1z}=[1z11]+[11z1]+[111z] forCH
3
{1z}=[1z1]+[11z] forCH
2
{1z}=[1z] forCH
Otherexamplesofthe{}notation:
{1x}=[1x1]+[11x] forCH
2
{zy}=[zy11]+[z1y1]+[z11y] forCH
3
The sum { } has always n terms where n is the number of magneti
cally equivalent nuclei. In order to be consistent we have to write
{z1}as:
{z1}=[z111]+[z111]+[z111]=3[z111] forCH
3
{z1}=2[z11] forCH
2
{z1}=[z1] forCH
The Multiplet Formalism 185
Withthisconventionwecanrewrite(L2)as:
(0) ( '/ ){ 1} '{1 } D p n z q z = ÷ ÷ (L3)
anexpressionvalidforany n.
Letusapplya90xXpulsetoD(0).
(L4)
90
(0) ( '/ ){ 1} '{1 }
xX
D p n z ÷÷÷÷÷ + q y
Theexpressionaboveiseasily obtainedthroughtheconventionalPO
rulesappliedtotheexpression(L1)oritsequivalentsforCH
2
orCH.
The above example may inspire us to hope that any sequence
involving a CH
2
or CH
3
system may be treated as a CH, just by
replacing [ ] with { }. Unfortunately this is not always true. It is
importantfortheuserofthisformalismtobeawareofhowfar the { }
notationscanbeusedandwhenwehavetogiveupandgo back to the
explicit[]notation.
Rule #1
NotallthePOsinthebasissetcanbeincludedin{}sums.For
instance [1xz] is not a legitimate term of such a sum. No more than
oneoftheprotonsmaycomeinthePOwithx, yorz,theothersmust
participatewitha1.
Rule #2
Rotationsduetor.f.pulsesdonotbreakthe{}formalismand
can be treated according to the vectorialmodel.Wehavedonethisin
(L4).
Rule #3
Likewise,noncoupledevolutions(whicharemerely zrotations)
canbetreatedaccordingtothevectorialrepresentation.Example:
{ } { }cos { }sin
shift X
X X
zx zx t zy t ÷÷÷÷ O + O
WecansatisfyourselvesthatthisistrueinthecaseofCH
2
:
{ } [ 1] [ 1 ] zx zx z x = +
[ 1]cos [ 1]sin [ 1 ]cos [ 1 ]sin
shift X
X X X
zx t zy t z x t z y ÷÷÷÷ O + O + O +
{ }cos { }sin
X X
zx t zy t = O + O
X
O
186 Appendix L
Rule #4
A coupled evolution usually breaks the { } formalism, since it
generates PO's that cannot be included in { } sums. A fortunate
exception we can take advantage of is presented by the sums: {1x},
{1y}, {zx}, {zy}. The coupled evolution of any of these sums does
not break the { } formalism and can be treated according to Section
II.7.
Rule #5
Ifthedensitymatrixcontainssumsas{x1},{yz}or{xy}anda
coupled evolution follows, we have to give up the { } shorthand and
gobacktotheregularPOformalism([]notation).
Even here there is an exception and it is worth talking about
because it maysavealotoftermwriting.Theexceptionworkswhen
the coupled evolution we are talking about is the last act of the
sequence orisjustfollowedbyadecoupledevolution.Inthiscasewe
are interested in the observable terms only (see Appendix K) and the
coupled evolution yields unexpectedly simple results (we observe
nucleusA):
{ 1} { 1} { 1} NOT
n n
x cC x sC y ÷÷÷ + +
{ 1} { 1} { 1} NOT
n n
y sC x cC y ÷÷÷÷ + +
1 1
{ } { 1} { 1} NOT
n n
xz sSC x cSC y
÷ ÷
÷÷÷÷ + +
1 1
{ } { 1} { 1} NOT
n n
yz cSC x cSC y
÷ ÷
÷÷÷÷ ÷ +
{ } NOT xx ÷÷÷
{ } NOT yx ÷÷÷
{ } NOT xy ÷÷÷
{ } NOT yy ÷÷÷
cos ; cos ; numberofprotons
sin ; sin ; nonobservableterms
C
C
c t C Jt n
s t S Jt NOT
t
t
= O = =
= O = =
The above evolution rules can be verified by writing the product
operatorsintheconventionalwayand calculatingtheevolutionofthe
CH
n
systemforn=1,2,and3,separately.
The Multiplet Formalism 187
Rule #6
The procedure for retrieving the magnetization components in
the{}formalismdiffersonlyslightlyfromthatstatedinAppendixJ.
( ) ( )
( ) (
/ ' coefficientof{ 1}
/ ' coefficientof {1 }
xC oC
xH oH
)
M nM p x
M M q x
= ÷ ×
= ÷ ×
(L5)
with similar expressions for M
y
and M
z
. M
oH
is the equilibrium
magnetizationduetoallnmagneticallyequivalentprotons.
188 Appendix M
APPENDIX M: ROTATIONS ABOUT
NONTRIVIAL AXES
Rotations due to r.f. pulses follow in the PO formalism the
pattern of vector kinematics. In Section II.6 we have discussed
rotationsabouttheaxes OxandOy.Inordertotreatthegeneralcase
(rotation axis with any spatial orientation) we use spherical
coordinatesasshowninFigureM.1.Therotationaxismakes an angle
T with Oz ( ) and its horizontal projection makes the
angle )withOx(positivesensefor)isfrom OxtowardOy).
o
0 180 T d d
)
T
'Z
rotation
axis
J B
1
D
x
y
z
Figure M.1.Rotationaxisinsphericalcoordinates.
If the r.f. pulseisappliedonresonance,T=90
o
.Foradeviation
'Z=JB
o
Z
tr
fromresonance,theangleT isdifferentfrom90
o
;its
value is defined by tanT = JB
1
/'Z. The angle ) is the transmitter
phase which is always taken with respect to an initially established
receiverphase.
TheresultofarotationbyanangleD(righthandrule)aboutthe
axisdefinedaboveisdescribedinTableM.1.
Rotations about Nontrivial Axes 189
Table M.1. FinalAngularMomentumComponentsafterRotationby
anAngleD abouttheRotationAxisDefinedbyAngles Tand).
Initial
com
ponent
Finalcomponents
I
x
(1 cos )
x
I D u
2 2
sin cos T u )
cos
x
I D
(1 cos )
y
I D u
2
sin cos sin T u ) )
sin cos
y
I D T
(1 cos )
z
I D u
sin cos cos T T u )
sin sin sin
z
I D T )
I
y
(1 cos )
x
I D u
)
2
sin cos sin T u )
sin cos
x
I D T
(1 cos )
y
I D u
2 2
sin sin T u )
cos
y
I D
(1 cos )
z
I D u
sin cos sin T T u )
sin sin cos
z
I D T )
I
z
(1 cos )
x
I D u
sin cos cos T T u )
sin sin sin
x
I D T )
(1 cos )
y
I D u
sin cos sin T T u )
sin sin cos
y
I D T )
(1 cos )
z
I D u
2
cos T u
cos
z
I D
190 Appendix M
InTableM.2weconsidertheparticularcaseofanonresonance
pulse(T=90
o
).
Table M.2.FinalAngularMomentumComponentsafterRotation by
an Angle D about an Axis in the xy Plane (T=90
o
) Defined by Angle
).
Initial
com
ponent
Finalcomponents
I
x
2
cos
x
I )
2
cos sin
x
I D )
(1 cos )
y
I D u
cos sin u ) )
sin sin
z
I D )
I
y
(1 cos )
x
I D u
cos sin u ) )
2
sin
y
I )
2
cos cos
y
I D )
sin cos
z
I D )
I
z
sin sin
x
I D ) sin cos
y
I D ) cos
z
I D
Rotations about Nontrivial Axes 191
Veryoftenthephaseangle)canonlytakeoneofthe"cardinal"
values0
o
,90
o
,180
o
,270
o
.Inthiscase,theproductsin)cos)
vanishesandtheexpressionsabovebecomeevensimpler,asshownin
TableM.3.
Table M.3.FinalAngularMomentumComponentsafterRotation by
anAngleD aboutanAxisinthe xyPlane(T=90
o
) withtheAngle )a
Multipleof90
o
.
Initial
com
ponent
Finalcomponents
I
x
2
cos
x
I )
2
cos sin
x
I D )
0
sin sin
z
I D )
I
y
0
2
sin
y
I )
2
cos cos
y
I D )
sin cos
z
I D )
I
z
sin sin
x
I D ) sin cos
y
I D ) cos
z
I D
Making ) equal to 0
o
, 90
o
, 180
o
, 270
o
, in Table M.3, yields the
rotation rules about Ox, Oy, Ox, Oy (phase cycling). It is
instructive to compare these results with those obtained by means of
thevectorrepresentation.
192 Suggested Readings
Suggested Readings
R.R.Ernst,G.BodenhausenandA.Wokaun,Principles of Nuclear
Magnetic Resonance in One and Two Dimensions,ClarendonPress,
Oxford,1987.
RayFreeman, A Handbook of Nuclear Magnetic Resonance,Longman
ScientificandTechnicalPublishingCo.,Essex,1988.
O.W.Sörensen,G.Eich,M.Levitt,G.BodenhausenandR.R.Ernst,
Progress in NMR Spectroscopy, 16,1983,163192.
AdBax,TwoDimensional Nuclear Mgnetic Resonance in Liquids,
ReidelPublishingCo.,Dordrecht/Boston/Lancaster,1982.
T.C.FarrarandJ.E.Harriman, Density Matrix Theory and Its
Applications in Spectroscopy,FarragutPress,Madison,WI,1991.
M.Goldman, Quantum Description of High Resolution NMR in
Liquids,ClarendonPress,Oxford,1988.
C.P.Slichter,Principles of Magnetic Resonance,SpringerVerlag,
Berlin/Heidelberg/NewYork,1980.
G.E.MartinandA.S.Zektzer,TwoDimensional NMR Methods for
Establishing Molecular Connectivity: A Chemist's Guide to
Experiment Selection, Performance and Interpretation,VCH
Publishers,Weinheim/NewYork,1988.
G.D.MateescuandA.Valeriu,"TeachingtheNewNMR:ACom
puterAidedIntroductiontotheDensityMatrixFormalismof
MultipulseSequences,"inSpectroscopy of Biological Molecules,
CamilleSandorfyandTheophileTheophanides(Eds.),Reidel
PublishingCo.,Dordrecht/Boston/Lancaster,1984,213256.
G.D.MateescuandA.Valeriu,"TeachingtheNewNMR:ACom
puterAidedIntroductiontotheDensityMatrixTreatmentof
DoubleQuantumSpectrometry,"in Magnetic Resonance,Leonidas
PetrakisandJacquesFraissard(Eds.),ReidelPublishingCo.,
Dordrecht/Boston/Lancaster,1984,501524.
Index 193
INDEX
A
Angularmomentum,1,6067,
69,116,120,121,125,
137142
Angularfrequency,9,46
APT, 102104
Acquisition,4,14,18,57,104
Argument,105107
Avram,19
Axis:
imaginary,105
real,105
rotation,188191
B
BASIC, 148,152,153158
Basisset,60,67,69,147,168
Boltzmann,60,124,180
distribution,5,32
Bra, 121,135
Buildingblock,59,60,67
C
Chemicalshift,23,32,38,65,98
Coherence,2,14,23
doublequantum,2,31, 36,
39,41,76
multiplequantum,76
singlequantum,2,8, 35,
36,37,39,41
zeroquantum,3,36,76
Commutativity,8,112
Commutationrules,59,172
Complexconjugate,9,49,105
Conjugation,7,37
Connectivity:
carboncarbon,43,44
Contourplot,17,20,42,50,51,
57,58
Correlation:
heteronuclear,4,17,20
homonuclear,45
COSY, 18,4559
Coupling,11,38,7678
constant,5,11,65
evolution,163167
longrange,20
weak,19,163
Cyclops,146
D
Decoupling,23,31
Densitymatrix,6066,116
definition,123
formalism,159,73,
120136
intuitivepicture,13
DEPT, 94101
Detection,16,42,49,57,104
quadrature,18,44,57
Determinant,114
Domain,43,49
Doublet,11,18,43,90,92
E
Effectivemagneticfield,130
Eigenfunctions,121,127,128,
130,134
Eigenstates,121
Energylevels,1,2,5,33
Enhancementfactor,17,26,83,
86,89
Ensemble,3,120,123
Ernst, 68
Evolution,4,9,3536,7476,
127129
coupled,6567,80,81,
169170
coupling,75,164167
decoupled,11,8283
shift,74,75,77,163
F
Fastscanning,87,89,95
194 Index
Frame:
laboratory,11,129
rotating,9,11,15,129
Fouriertransform,16,17,59
G
Gyromagneticratio,1,182
H
Hamiltonian,116,129
Hardware, 59,162
Hermitianmatrix,8,48,116,125
HETCOR, 69
DMtreatment,430,
174179
POtratment,8083
ofCH
2
andCH
3
,8386
I
Imaginaryunit,105
Imbalance,25
INADEQUATE, 3144,59,145
INEPT, 8793,94
K
Ket, 2,121
L
Label, 74
change,11,23,38
fast/slow,11,22,23,38
Larmorfrequency,5,101
M
Magneticmoment,1,120
Magneticqantumnumber,2,35,
62
Magnetization,3,18,33,120,
123126
components,3,21,25, 85
180182
equilibrium,41
longitudinal,23,25,41
transverse,16,22,23,41
observable,4,81
Magnitudecalculation,17,58
Matrix,121,122
addition,110
adjoint,116
algebra,109116
derivative,136
elements,49,59,139
diagonal,127
observable,55
nondiagonal,127
Hermitian,8,48,116,125
inversion,112114
multiplication,110111
postmultiplication,8,63
63
premultiplication,8,14,63
trace,15,48,126,147
unit,6,61,69,70
Modulation,25,26,29
amplitude,16,44,49
phase,44,56,57
Modulus,105,106
Multiplet,18,90,93
formalism,83,88,95,
184187
illresolved,58
N
Nenitzescu, 19,20
Nonobservableterms(NOT),
81,97,183
Normalization,6,180
O
Observable, 14,88
Operators:
evolution,6
rotation,7,10,24,34,
116,133,137146,161
Overlap, 20,58
Index 195
P
Peak:
axial,44
cross,57
diagonal,57
neardiagonal,57
offdiagonal,57
Phasecycling,18,31,40,42,
5159,99,144146,191
Polarizationtransfer,1,17,24,
80,88,89,94
Population,3,8,61,127
difference,7
equilibrium,5,32,45
inversion,10
Productoperator(PO),59,
147152,161,180182
definition,6769
formalism,6079
treatment,80104
Pulse, 4,7,37,62,129134
nonselective,13,34,71,73
sequence,4,31,45,52,
53,87,94,102
Q
Quadraturedetection,18,51,57
Quartet,92,93
R
Receiverphase,31,42,99,188
Recycletime,95,100
Refocusing,38,171173
routine,11,7780,84,88
Relaxation,9,87,94
Repetitionrate,88
Righthandrule,182,188
Rotation,7073,82,106,107,
159162,188191
Rule(s):
commutation,159
coupledevolution,163
couplingevolution,76
multipletformalism,84,
85,95,185187
nonobservableterm,183
refocussingroutine,77,
171
shiftevolution,74
S
Satellites, 31
Schrödinger,120,121,127
Sequence, 4,31,45,52,53,87,
94,102
Seriesexpansion,5,108,109,
131,133
Shift:
chemical,23,32,38,65,98
evolution,163
Shorthand,59,62,64,69
Shortcut,7779,114
Signconvention,1,64,124,182
Slichter,134
Stackplot,20
T
Thermalequilibrium,5,32,34,
87,126
Trace, 15,48,126,147
Transitionfrequency,2,5,32,35
Transmitter,18,51
frequency,9,44
Transposition,7,112,116
Triplet,92,93
V
Vectorrepresentation,1,2130,
33,35,39,40,64,7074,
102,104
W
Wavefunction,120123
2D NMR
Density Matrix
and
Product Operator Treatment
Gheorghe D. Mateescu and Adrian Valeriu
Department of Chemistry Case Western Reserve University Cleveland, Ohio
To the memory of our teachers and parents
Contents
Foreword Preface Acknowledgements Part I. The Density Matrix Formalism 1. 2. 3. Introduction The Density Matrix The Density Matrix Description of a TwoDimensional Heteronuclear Correlation Sequence (2DHETCOR) 3.1 Calculation Steps 3.2 Equilibrium Populations 3.3 The First Pulse 3.4 Evolution from t(1) to t(2) 3.5 The Second Pulse 3.6 Evolution from t(3) to t(4) 3.7 The Role of 1 3.8 Third and Fourth Pulses 3.9 The Role of 2 3.10 Detection 3.11 Comparison of the DM Treatment with Vector Representation The Density Matrix Description of a DoubleQuantum Coherence Experiment (INADEQUATE) 4.1 Equilibrium Populations 4.2 The First Pulse 4.3 Evolution from t(1) to t(2) 4.4 The Second Pulse 4.5 Evolution from t(3) to t(4) 4.6 The Third Pulse 4.7 Evolution from t(5) to t(6) 4.8 The Fourth Pulse 4.9 Detection 4.10 CarbonCarbon Connectivity v 1 1 4 4 5 7 9 10 11 11 13 14 16 21 31 32 34 35 37 38 39 39 40 42 43 x xi xiii
4.
4 The Second Pulse 5. 7 Part II. Introduction Expressing the Density Matrix in Terms of Angular Momentum Components Describing the Effect of a Pulse inTerms of Angular Momenta An Unsuccessful Attempt to Describe a Coupled Evolution in Terms of Angular Momenta Product Operators (PO) Pulse Effects (Rotations) in the Product Operator Formalism 60 60 3.3 Detection Conclusion of Part I 45 45 46 46 46 49 52 52 53 57 59 6. 65 67 5 6. The Product Operator Formalism 1.vi Contents 5.3 Evolution from t(1) to t(2) 5. . Treatment of Evolutions in the Product Operator Formalism Refocusing Routines 74 77 8. 2.1 Comparison with the Previous Sequence 6.1 Equilibrium Populations 5.5 Detection COSY with Phase Cycling 6.2 The First Pulse 5. 70 7.2 The Second Pulse 6. Density Matrix Description of COSY (Homonuclear COrrelation SpectroscopY) 5. 62 4.
M. 94 102 14. 11. I. D. E. K. 13. H. L. F. Appendices Math Reminder Density Matrix Formalism Angular Momentum and Rotation Operators Properties of Product Operators Demonstration of the Rotation Rules Demonstration of the Coupled Evolution Rules PO Evolution Tables Demonstration of the Refocusing Rules Supplementary Discussions Product Operators and Magnetization Components When to Drop Nonobservable Terms (NOT) Magnetic Equivalence: The Multiplet Formalism Rotations about Nontrivial Axes 105 120 137 147 159 163 169 171 174 180 183 184 188 192 193 Suggested Readings Index . A. C. PO Treatment of 2DHETCOR: Two Spins (CH) PO Treatment of 2DHETCOR: CH2 and CH3 PO Treatment of a Polarization Transfer Sequence: INEPT (Insensitive Nuclei Enhancement by Polarization Transfer) with Decoupling Coupled INEPT PO Treatment of DEPT (Distortionless Enhancement Polarization Transfer) PO Treatment of APT (Attached Proton Test) 80 83 87 89 12.Contents vii 9. B. 10. J. G.
Those who master a mathematical description of NMR experiments have an enormous advantage over users who blindly follow the rules of the instruction manuals. This formalism is like a magic key that provides access to the enormous arsenal of NMR techniques available today and permits the user to select and properly apply the most suited tools as well as to develop himself novel. Ernst Asilomar. The most elegant. Its versatility and its range of applications is truly unlimited. and also most intuitive description developed so far is the product operator formalism that is the central subject treated in this book.Foreword There is hardly any doubt that NMR is nowadays the most powerful and perhaps also the most beautiful analytical technique. NMR is unique in the sense that it derives its power largely from a quantum mechanical understanding of its foundations. April 1992 viii . Mateescu and Adrian Valeriu will serve its purpose exceptionally well in the hands of numerous novices that intend to enter this fascinating field of science. techniques. Richard R. I am convinced that this pedagogically very well done book by Gheorghe D. perhaps even more useful. most simple.
This book constitutes a guide for the use of density matrix calculations in the description of multipulse NMR experiments. This section is written in such a way as to be accessible to students with only an undergraduate mathematical background (there is even a Math Reminder in Appendix A). the text follows a stepbystep procedure which contains more detail than usual. including handwaving. It starts with the characterization of the system of nuclei at equilibrium in a magnetic field and concludes with the calculated signal which results from application of pulses and evolutions. the density matrix (DM) formalism. The quantum mechanical approach is deferred to Appendix B. constitutes a significant barrier for a growing number of students and scientists in the fields of chemistry. It thus became necessary to use an appropriate tool. 2DHETCOR (2D heteronuclear correlation).Preface Until recently. In order to ensure the continous flow of the minimal information needed to understand the sequence without too many sidetracks a number of detailed calculations of secondary importance are given in Appendix I. since the pulse sequences were relatively simple. The advent of twodimensional NMR made it practically impossible to explain the intricate effects of combined pulses and evolutions exclusively on the basis of vector representation. Our treatment begins with an intuitive representation of the density matrix and continues with matrix calculations without trying to explain the quantum mechanical origin of pulse effects (rotations) and evolution of the matrix elements. In keeping with its didactic nature. however. The DM treatment is generally found in specialized books which emphasize its quantum mechanical foundation. The quantum mechanical approach. Those who do not want to take anything for granted may actually begin with Appendix B (it is assumed. This will give readers with modest mathematical background the possibility to work out or to create sequences of various degrees of complexity. that the reader is familiar with the principles and experimental aspects of Fourier transform NMR). The first part of the book contains a detailed DM description of the popular twodimensional sequence. of course. the teaching and understanding of modern (pulse) Nuclear Magnetic Resonance has made successful use of vector descriptions. ix . biology. medicine and materials research who want to gain a better understanding of 2D NMR.
through the calculations of a doublequantum coherence sequence and those of the widely used COSY (correlation spectroscopy). Being essentially a selfsufficient teaching tool (lecture notes). and Interpretation. the student is led. Performance. there is still no consensus as to what notation should be given to the detection period (some call it t1. One of us being a passionate skier. Appendices E through M are for students interested in a demonstration of the relations and procedures used in the text. stepbystep.in order to avoid confusion with the relaxation times T1 and T2. this book does not contain literature references. He or she will be able to handle in reasonable time and space systems of more than two nuclei which would require much more elaborate calculations via the unabridged DM treatment. The teaching method presented in this book has been successfully used in an Instrumental Analytical Chemistry graduate course for the past few years at Case Western Reserve and in several short courses. Appendix B offers an accessible quantum mechanical presentation of the density matrix. Numerous citations can be found in the books indicated in the Suggested Readings section. The second part is entirely dedicated to the product operator (PO) formalism. In fact. we may say our class is for beginners. Throughout the book. for intermediates. The student will appreciate the significant economy of time provided by this elegant condensation of the density matrix procedure. Appendix C contains a selection of angular momenta and rotation operators written in matrix form.x Preface Once familiar with 2DHETCOR. and ErnstBodenhausenWokaun's. for advanced. while Appendix D summarizes the properties of product operators. this does not affect the essential features of the calculated 2D spectra and contributes to the clarity of the presentation. Throughout this book we did not use the t1 and t2 notations for the two time variables in a 2D experiment. some t2). x . our work is a synergic complement to Martin and Zektzer's TwoDimensional NMR Methods for Establishing Molecular Connectivity: A Chemist's Guide to Experiment Selection. Also. Farrar and Harriman's. relaxation processes have been neglected.
xi . We also thank Frank Anet of UCLA and Gary Martin of the Burroughs Welcome Co. Claudia and Anca. The first presentations of our way of teaching the density matrix formalism was at two NATO Advanced Study Institutes organized in 1983 by Camille Sandorfy and Theophile Theophanides in Italy and by Leonidas Petrakis and Jacques Fraissard in Greece. and the wonderful copyeditor Mary Russell. Our publishing team has done an excellent job and we wish to thank Sidney Solomon and Raymond Solomon of the Solomon Press. Betty Sun of Prentice Hall. for their comments and encouragement. published by D. but not least. Reidel Publishing Company (listed in the Suggested Reading Section).Acknowledgments We thank Guy Pouzard and Larry Werbelow of the Université de Provence (Marseille) for stimulating discussions which inspired our endeavor. We thank for permission to use material from those papers. we acknowledge the loving care and understanding of our spouses. Last.
with its four energy levels E1 to E4 (Figure I. 1 . We assume here (and throughout the book) a negative gyromagnetic ratio. After becoming familiar with the use of the density matrix as a tool. A and X. Even some onedimensional NMR sequences (see Part II. the reader may find enough motivation to go to Appendix B which deals with the quantummechanical meaning of the density matrix. INTRODUCTION Only the simplest NMR pulse sequences can be properly described and understood with the help of the vector representation (or handwaving) alone.12) defy the vector treatment because this approach cannot account for the polarization transfer. This explains the spin angular momentum orientation against the field in the lowest energy level E4. THE DENSITY MATRIX Before entering the formal treatment of the density matrix (see Appendix B) let us build an intuitive picture. in this state the magnetic moment is oriented with the field. The goal of Part I is to show how the density matrix can be used to understand a specific NMR pulse sequence. Of course.1) generally described in introductory NMR textbooks. 2. All twodimensional experiments require the density matrix formalism. We begin with the simple system of two spin 1/2 nuclei.1 The Density Matrix Formalism 1. A "math reminder" is given in Appendix A for those who may need it.
1. are shown in Table I. There is also one doublequantum coherence. in the transition only the nucleus A is flipped. 2QAX.1 (we assign the first symbol in the ket to nucleus A and the second. m. . These matrix elements are called "coherences" (for a formal definition see Appendix B) and are labeled according to the nature of the transitions between the corresponding states. This is the general form of the density matrix for the system shown in Figure I. . The corresponding matrix element will represent a single quantum coherence implying an A transition and will be labeled 1QA. It can be seen that the offdiagonal elements of the matrix connect pairs of different states.1. Transition (precession) frequencies A and X and the coupling constant J are expressed in Hz. they are mirror images of the ones indicated above the diagonal). For instance.J/2 E1 A + J/2 E2 X 0 ( ) A ) A . Energy levels of an uncoupled (left) and coupled (right) heteronuclear AX system. The possible connections between the four quantum states represented by the "kets" . We thus find two 1QA and two 1QX coherences (the matrix elements on the other side of the diagonal do not represent other coherences. . The first column contains the total magnetic quantum number. to nucleus X).2 Density Matrix Treatment +1 0 ( ( ) A ) X + J/2 X X .J/2 E3 E4 1 ( m AX Figure I. .
as we will see later. The extra information contained in the density matrix enables us to understand the NMR sequences which cannot be fully described by vector treatment. Populations and macroscopic magnetizations can be derived from the elements of the density matrix. The reciprocal statement is not true: given the magnetization components and populations we do not have enough information to write all the elements of the density matrix. The zeroquantum coherence ZQAX can be considered as representing a flipflop transition E2 E3. . Translation of the Classical Representation of a Twospin System into a Density Matrix Representation AX P1 1Q A 1Q X 2Q AX P2 ZQ AX 1Q X P3 1Q A P4 The density matrix contains complete information about the status of the ensemble of spins at a given time. Table I. The diagonal elements represent populations.Introduction to Density Matrix 3 related to the transition . The name of this coherence does not necessarily imply that the energy of the transition is zero.1.
g. This is based on the scalar coupling interaction between the two spins. 3.evolution between pulses .2 reveals that the density matrix treatment of a pulse sequence must include the following calculation steps: .4 Density Matrix Treatment 3.thermal equilibrium populations (off diagonal elements are zero) . nucleus X is a proton) we will describe in detail each of these steps.determination of observable magnetization..1 Calculation Steps Figure I.effects of rf pulses (rotation operators) . 90xH 1H 180xC 13 90xC t e /2 1 2 90xH Decouple C t e /2 td t(0) t(1) t(2) t(3) t(4) t(5) t(6) t(7) t(8) t(9) Figure I. THE DENSITY MATRIX DESCRIPTION OF A TWODIMENSIONAL HETERONUCLEAR CORRELATION SEQUENCE (2DHETCOR) The purpose of 2DHETCOR is to reveal the pairwise correlation of different nuclear species (e.2. 1 2 . Applying the sequence to an AX system (nucleus A is a 13C. The twodimensional heteronuclear correlation sequence: 90xH te /2 180xC te /2 90xH 90xC AT.evolution during acquisition . CH or CF) in a molecule.
7 Tesla magnet the 13C Larmor frequency is = 50 x 106 Hz and p h A kT 6.1 are populated according to the Boltzmann distribution law: Pi Pj exp( Ei / kT ) exp( E j / kT ) exp Ej kT Ei (I. in a 4.2DHETCOR 5 3. We now normalize the sum of populations: .3) (I. they will not be neglected when calculating transition frequencies). of course..4 10 23 (J/K) 300K 0. q = 4p).5) X X P4 / P 1 [h( 1 A ) / kT ] 1 p q In the particular case of the carbonproton system the Larmor frequencies are in the ratio 1:4 (i.2) Since transition frequencies (108 Hz) are more than six orders of magnitude larger than coupling constants (tens or hundreds of Hz). Furthermore. we may neglect the latter (only when we calculate relative populations. the ratios h A/kT and h X/kT are much smaller than 1.2 Equilibrium Populations At thermal equilibrium the four energy levels shown in Figure I. For instance.1) Taking the least populated level as reference we have: P2 / P 1 exp[( E1 E2 ) / kT ] exp[h( A J / 2) / kT ] (I.785 10 5 This justifies a first order series expansion [see (A11)]: P2 / P 1 P3 / P 1 exp(h exp(h A / kT ) 1 (h / kT ) 1 (h X A / kT ) 1 p / kT ) 1 q (I.6 10 34 Js 50 106 s 1 1.4) (I.e.
Then the density matrix at equilibrium is: D 0 P1 0 0 P2 0 0 0 0 0 0 0 0 P3 0 0 P4 1 1 0 4 0 0 0 1 0 0 0 0 1 0 1 4 1 0 0 0 0 p 0 4 0 0 0 1 p 0 0 0 1 0 0 0 0 4 0 0 0 1 4p 0 1 0 0 0 5 0 0 0 5p 0 0 0 1 It is seen that the first term of the sum above is very large compared to the second term. the first term is not important since it contains the unit matrix [see (A20)(A21)] and is not affected by any evolution operator (see Appendix B). it is the second term which counts because it contains the population differences (Vive la difference!). P 1/ S 1 P2 (1 p ) / S P3 P4 (1 4 p ) / S (1 5 p) / S where S 4 10 p Given the small value of p we can work with the approximation S 4.6 Density Matrix Treatment P 1 P2 P3 P4 P 1 (1 p ) P 1 (1 4 p ) P 1 (1 5 p) P 1 PS 1 (I. Though much smaller. However.6) ____________________ 1 P (4 10 p) 1 Hence. From now on we will work with this .
it is necessary to specify that we postmultiply D(0) by R: .9) where i 1 is the imaginary unit. particular case is [see (C18)]: The rotation operator.8) is explained in Appendix B.2DHETCOR 7 term only. D(1) = R1 D(0) R. for this R90 xH 1 0 i 0 1 0 1 0 i 2 i 0 1 0 0 i 0 1 (I.10) First we multiply D(0) by R. ignoring the constant factor p/4 and taking the license to continue to call it D(0): D(0) 0 0 0 0 0 1 0 0 0 0 4 0 0 0 0 5 (I. 3. Since the matrix multiplication is not commutative (see Appendix A for matrix multiplication rules). the density matrix after the pulse.7) Equilibrium density matrices for systems other than CH can be built in exactly the same way. (I.3 The First Pulse At time t(0) a 90o proton pulse is applied along the xaxis. Its inverse (reciprocal). We now want to calculate D(1). is readily transposition and conjugation [see (A22)(A23)]: calculated by R901xH 1 1 0 2 i 0 0 1 0 i i 0 1 0 0 i 0 1 (I. R. R1. The standard formula for this operation.
. nor the partial results need be Hermitian). Comparing D(1) to D(0) we see that the 90o proton pulse created proton singlequantum coherences. and redistributed the populations. did not touch the carbon. i.8 Density Matrix Treatment D(0) R 0 0 0 0 0 1 0 0 0 0 4 0 0 0 0 5 1 0 i 0 1 0 1 0 i 2 i 0 1 0 0 i 0 1 0 0 4 0 0 i 0 5 0 0 1 0 1 2 4i 0 0 5i Then we premultiply the result by R 1 : (I. every matrix element below the main diagonal is the complex conjugate of its corresponding element above the diagonal [see (A24)] (neither the rotation operators.e.11) D(1) R 1 [ D(0) R] 1 1 0 2 i 0 4i 0 4 0 0 4i 0 6 0 1 0 i i 0 1 0 2 0 2i 0 0 i 0 1 0 3 0 2i 0 0 1 0 1 2 4i 0 0 5i 2i 0 2 0 0 2i 0 3 0 0 4 0 0 i 0 5 4 1 0 2 4i 0 0 6 0 4i (I. .12) It is good to check this result by making sure that the matrix D(1) is Hermitian.
relaxation during the pulse sequence is ignored. Note that dmn(0) is the starting point of the evolution immediately after a given pulse. the elements dmn(0) are those of D(1). In the present case. after an evolution time te/2. We have to consider the evolution of elements d13 and d24.4 Evolution from t (1) to t (2) The standard formula1 describing the time evolution of the density matrix elements in the absence of a pulse is: d mn (t ) d mn (0) exp( i mn t) (I. 1In our treatment. This contributes to a significant simplification of the calculations without affecting the main features of the resulting 2D spectrum. .2. The off diagonal elements experience a periodic evolution. D (2) 2 0 0 3 B* 0 0 C* B 0 2 0 0 C 0 3 (I. In a frame rotating with the proton transmitter frequency trH. We now want to calculate D(2) at the time t(2) shown in Figure I.15) .14) (I.2DHETCOR 9 3. We observe that during evolution the diagonal elements are invariant since exp[i(Em Em)/ ] = 1. column n) and mn=(Em En)/ is the angular frequency of the transition m n. their values are: d13 d 24 where Hence 13 13 trH 2i exp( i 2i exp( i and 24 24 13 e t / 2) B C 24 te / 2) trH (I.13) dmn is the matrix element (row m.16) B* and C* are the complex conjugates of B and C (see Appendix A).
after having evolved with the frequency 13 during the first half of the evolution time [see (I.18) Postmultiplying D(2) by R gives: D(2) R180 xC 0 3i 0 iC * 2i 0 i 0 0 iC iB * 3i iB 0 2i 0 (I. . It has also interchanged the coherences B and C (d13 and d24). will now evolve with the frequency 24. R180 xC 0 i 0 0 i 0 0 0 0 0 0 i 0 0 i 0 (I.19) by R 1 gives: D(3) 3 0 0 2 C* 0 0 B* C 0 3 0 0 B 0 2 (I. while C switches form 24 to 13.17).14)].10 Density Matrix Treatment 3.19) Premultiplying (I.20) Comparing D(3) with D(2) we note that the 180o pulse on carbon has caused a population inversion (interchange of d11 and d22). This means that B.5 The Second Pulse The rotation operators for this pulse are [see(C17)]: R180 xC 0 i 0 0 i 0 0 0 0 0 0 i 0 0 i 0 1 (I.
i. We call the sequence te/2 . 3.23) (I.13) the elements d13and d42 become: d13 d 24 C exp( i B exp( i 13 e t / 2) 24 te / 2) (I. The protons which were fast ( 13) during the first te/2 are slow ( 24) during the second te/2 and vice versa (they change label).22) become d13 d 24 2i exp[ i ( H J )te / 2]exp[ i ( 2i exp( i H te ) 2i exp( i H te ) d13 H J )te / 2] (I. The result looks like that of a decoupled evolution.21) (I.21) and (I. d13 and d24 must be equal but of opposite signs. relations (I.14) and (I.24) Taking the In the rotating frame (low case) becomes (capital) expressions of B and C from (I.2DHETCOR 11 3. with d13=d24.6 Evolution from t (3) to t (4) According to (I. This is what the delay 1 enables us to achieve. To obtain maximum signal.7 The Role of 1 In order to understand the role of the supplementary evolution 1 we have to carry on the calculations without it.15). We know that the coupling J was actually present during the evolution. as documented by the intermediate results D(2) and D(3).180C . .26) None of the matrix elements of D(4) contains the coupling constant J.25) (I.. We find out (see Appendix I) that the useful signal is canceled.1 we see that in the laboratory frame 13 24 2 ( 2 ( X X J / 2) J / 2) H H J J (I. The (center frequency of the doublet) is expressed while averaged shift the coupling is not.22) From Figure I.te/2 a refocusing routine.e.
12 Density Matrix Treatment Evolution during 1 yields: d13 ( 5 ) d13 ( 4 ) exp( i 13 1 ) 2 i exp( i H te ) exp[ i ( H J ) 1] 2 i exp[ i H ( te )]exp( i J 1 ) 1 2 i exp[ i H ( te 1 )]exp( (I.27) d24 ( 5 ) i J 1) (I.30) 1 )] For the following calculations it is convenient to use the notations c s cos[ sin[ H ( te H ( te 1 )] (I. cos( / 2 ) i sin( / 2 ) exp( i J exp( i J 1) 1) i i (I.31) 1 )] which lead to d13 ( 5 ) d24 ( 5 ) 2(c 2(c is ) (I.29) i We now have d13 ( 5 ) d24 ( 5 ) 2 exp[ i 2 exp[ i H ( te H ( te 1 )] (I. which implies J 1= /2.32) is ) .28) To achieve our goal we choose Using the expression [see (A16)] exp( i / 2 ) 1=1/2J.
R90 xCH R90 xC R90 xH 1 2 0 0 1 i 0 0 i 1 1 1 i 2 i 1 The reciprocal of (I.33) 3.8 Third and Fourth Pulses Although physically these pulses are applied separately. we may save some calculation effort by treating them as a single nonselective pulse.34) R901xCH 1 1 i 2 i 1 i 1 1 i i 1 1 i 1 i i 1 .2DHETCOR 13 At this point the density matrix is: D(5) 3 0 2(c is ) 0 0 2 0 2(c is ) 2(c is ) 0 3 0 0 2(c is ) 0 2 (I.34) is: 1 i 0 0 i 1 0 0 1 2 i 0 1 0 0 i 0 1 i 1 1 i i 1 1 i 1 i i 1 1 0 i 0 0 1 0 i (I. The expressions of R90xC and R90xH are taken from Appendix C.
to follow the evolution of the carbon coherences d12 and d34 which constitute the observables in this sequence. . carbon coherences are created in d12 and d34 due to the 90xC pulse. It is therefore sufficient. as expected. Second. the observable signal is proportional to the sum d12 + d34. Since no r. the proton information [s = sin H(te + 1)] has been transferred from d13 and d24 into the carbon coherences d12 and d34. pulse follows after t(7). the terms containing s would be cancelled. from now on. First.9 The Role of 2 As we will see soon.13). If we started the decoupled acquisition right at t(7).35) Comparing D(7) with D(5) we make two distinct observations. we allow for one more short coupled evolution 2. which are d12 d 34 i 4 is 2 i 4 is 2 This is an important point of the sequence because now the mixed carbon and proton information can be carried into the final FID. 3.f. we know that every matrix element will evolve in its own box according to (I. To save them.14 Density Matrix Treatment D ( 5 ) R90 xCH 3 1 2i 2 3i 2 2i (c 2(c 2(c 2i (c is) is) is ) is) 3i 2 3 2i 2(c 2i (c 2i (c 2(c is ) is ) is) is) 3i 2 3 2i 2(c 2i (c 2i (c 2(c is ) is) is) is) 3 2i 3i 2 2i (c 2(c 2(c 2i (c is ) is) is ) is ) Premultiplying the last result by R901xCH gives 5 D(7) 1 2 i 4is 0 4ic i 4is 5 4ic 0 0 4ic 5 i 4is 4ic 0 i 4is 5 (I.
at t(8) coherences d12 and d34 become d12 ( 8 ) i (1 / 2 d 34 ( 8 ) i (1 / 2 2 s ) exp( i 2 s ) exp ( i 12 34 2) 2 ) (I.39) Hence.13).40 41) we see that for 2 = 0 the terms in s which contain the proton information are lost when we calculate the sum of d12 and d34 As discussed previously for 1.37) where 12 = 12 trC and 34 = 34 trC indicate that now we are in the carbon rotating frame.38) (I. As shown in Figure I. here also. which leads to exp( i J 2) = i and d12 ( 8 ) d34 ( 8 ) (1 / 2 2 s ) exp( i (1 / 2 2 s ) exp( i C C 2) 2) (I. which is necessary to describe the carbon signal during the free induction decay.36) (I.43) .2DHETCOR 15 According to (I.40) (I.1 the transition frequencies of carbon (nucleus A) are: J J A C 12 2 2 J J A C 34 2 2 Since =2 .41) Analyzing the role of 2 in (I. d12 ( 8 ) i (1 / 2 2 s ) exp( i d34 ( 8 ) i (1 / 2 2 s ) exp( i C C 2 ) exp( i J ) exp( i J 2 2) 2) (I.42) (I. and we are in rotating coordinates we obtain: 12 34 C C J J (I. the desired signal is best obtained for 2 = 1/2J.
We must now reintroduce the factor p/4 which we omitted.49) represents the final result of our 2DHETCOR analysis by means of the density matrix formalism and it contains all the information we need.7)..47) we obtain MTC 4 MoC s exp( i C 2 ) exp( i C td ) (I.46) into a simpler form: * * MTC MoC ( d12 d34 ) (I.31): MTC 4 MoC sin[ H ( te 1 )]exp( i C 2 ) exp( i Ctd ) (I.e. representing the ratio.46) The transverse magnetization MT is a complex quantity which combines the x and y components of the magnetization vector. The signal is enhanced by a factor of four.44) (I.49) Equation (I. both d12 and d34 evolve with the frequency C: d12 ( 9 ) d34 ( 9 ) (1 / 2 2 s ) exp( i (1 / 2 2 s ) exp( i C C 2 ) exp( i 2 ) exp( i C td ) Ctd ) (I.4445). This is done by using the relations (B19) and (B20) in Appendix B: MTC MxC iMyC * ( 4 MoC / p )( d12 * d34 ) (I.47) By inserting (I. have brought us to the relations (I.49) that the carbon magnetization rotates by Ctd while being amplitude modulated by the proton evolution Hte. Fourier transformation with respect to both time domains will yield the twodimensional spectrum. i.45) Our density matrix calculations.16 Density Matrix Treatment 3. This allows us to rewrite (I. carried out for every step of the sequence. The polarization transfer achieved in 2DHETCOR and C . for convenience.48) With the explicit expression of s (I. starting with (I. Now it is time to derive the observable (transverse) carbon magnetization components. We learn from (I.10 Detection From the time t(8). on the system is proton decoupled.4445) into (I.
all factors other than sin[ H(te + 1)] are regarded as constant. A single peak frequency. During the . C. H H 13 H 24 24 H 13 0 C 0 C 0 C 24 H 13 24 13 C C 34 12 (a) (b) (c) Figure I. is obtained. Schematic 2D heteronuclear correlation spectra (contour plot): (a) fully decoupled. Since ei e i (I. With the usually employed magnitude calculation (absolute value). all peaks are positive.2DHETCOR 17 other heteronuclear pulse sequences cannot be explained by the vector representation. and (c) fully coupled. When transforming with respect to te.7 of the book by Martin and Zektzer (see Suggested Readings). Imagine now that in the sequence shown in Figure I. See experimental spectra in figures 3.9 and 3.50) sin 2i both H and H are obtained (Figure I.3a). (b) proton decoupled during the acquisition. During the evolution time te the proton is coupled to carbon.11.2 we did not apply the 180o pulse on carbon and suppressed 1. When transforming with respect to td. Filled and open circles represent positive and negative peaks. 3. all factors other than exp(i Ctd) are regarded as constant.3.
the proton may be coupled to one or several other protons. the proton transmitter can be positioned at midspectrum as well. provided quadrature phase detection is used.18 Density Matrix Treatment acquisition. The lower part of the spectra is not displayed by the instrument.49) we can explain the spectrum shown in Figure I. along the proton axis. In the sequence shown in Figure I. If such a pulse sequence is used.2 there is no protonproton decoupling. if we also suppress the decoupling during the acquisition and the delay we obtain (see Appendix I) MTC iMoC (1 / 2 cos iMoC (1 / 2 cos 13te 13te cos cos 24te ) exp( i 24te ) exp( i 12td ) 34td ) (I. So far we have treated the AX (CH) system.3c. the carbon is decoupled from proton.51) Reasoning as for (I. An example is given in Figure I. but proper care must be taken to place the proton transmitter beyond the proton spectrum. but multiplets corresponding to protonproton coupling. Such a requirement is not imposed on the carbon transmitter. The result (see Appendix I) is that along the carbon axis we see a single peak. involving phase cycling. Finally.4a which represents the high field region of the 2DHECTOR spectrum of a molecule . In reality. An example of achieving quadrature detection in the domain te is given in Section 6 (COSY with phase cycling). while along the proton axis we see a doublet due to the protoncarbon coupling.3b.52) which yields the spectrum shown in Figure I. The peaks in the lower part of the contour plot (negative proton frequencies) can also be eliminated if a more sophisticated pulse sequence is used. The 2D spectrum will therefore exhibit single resonances along the carbon axis. we find: MTC 2 MoC (cos 13te cos 13te ) exp[ i C ( td 2 )] (I. If we calculate the magnetization following the procedure shown before.
Nenitzescu. The high field region of the 2DHETCOR stack plot of a Nenitzescu’s hydrocarbon derivative in CDCl3 (at 50 MHz for 13C). the methyl group.Figure I. The peaks corresponding to the carbonyls. Mateescu and C.D. unpublished work).4a. Avram. 2DHETCOR 19 . and the carbon in position 9 are at lower fields (M. G.D.
4a.4b. Thus. Contour plot of the spectrum in Figure I.2. signals coming from long range couplings will have very small intensities. The delays 1 and 2 were set to 3.6 ms in order to optimize the signals due to 1J ( 140 Hz).9triene (Nenitzescu's hydrocarbon).4a.5]deca3. It shows in a more dramatic manner the advantage of 2D spectroscopy: the carbonproton correlation and the disentangling of the heavily overlapping proton signals.7.02. formally derived from [4. . For any other values of J the signal intensity is proportional to sin2 J .20 Density Matrix Treatment Figure I.49) has been derived with the assumption that 1 = 2 = = 1/2J.2. Figure I. It should be noted that the relation (I.4b is a contour plot of the spectrum shown in Figure I.
11 Comparison of the DM Treatment with Vector Representation It is now possible to follow the 2DHETCOR vector representation (Figures I. Indeed. Also.6d) and identify each step with the corresponding density matrix.2DHETCOR 21 3. consistent with the fact that no pulse has been applied.7) we find MzC MzH ( MoC / 2 )( 0 1 4 ( MoH / 8 )( 0 5) MoC MoH 4 1 5) (I. we obtain MzC MzH MTC MTH ( MoC / 2 )( d11 ( MoH / 8 )( d11 * MoC ( d12 * d34 ) * ( MoH / 4 )( d13 d22 d33 * d24 ) d33 d22 d44 ) d44 ) (I.6a through I.7). As demonstrated in Appendix B (see B15B22) the magnetization components at any time are given by: MzA MzX MTA MTX ( 2 MoA / p )( d11 ( 2 MoX / q )( d11 * ( 4 MoA / p )( d12 * ( 4 MoX / q )( d13 d22 d33 * d34 ) * d24 ) d33 d22 d44 ) d44 ) (B15) (B21) (B20) (B22) Considering the simplification we made in (I.53) We will use the relations (I. with the matrix elements of D(0) (see I. . It will be seen that one cannot draw the vectors for the entire sequence without the knowledge of the DM results.54) The transverse magnetizations MTC and MTH are both zero (all offdiagonal elements are zero). we must multiply the expressions above with the factor p/4. remembering that for the CH system q = 4p.53) throughout the sequence in order to find the magnetization components from the matrix elements. At time t(0) the net magnetization is in the zdirection for both proton and carbon.
Immediately after the 90xH pulse proton coherences were created.5. Therefore.54). carbons in states 1 and 2 are fast.J/2 s f s s ( ( ) A ) A . it is 12 and 34.12) we obtain: MTH ( MoH / 4 )( 2 i 2i ) iMoH . at t(0) half of MzH is due to fast protons (d11 d33) and the other half to slow protons.5 shows that the spins become faster or slower by J/2 Hz.6 with 13 and 24. they are fast.e. Speaking of CH pairs.. It is seen that protons in states 1 and 3 cannot be involved but in the higher frequency transition 1 3. Likewise. we will now define fast and slow components using Figure I. The fast and slow components of the proton magnetization are marked in Figure I. C H CH ( ( ) ) A f f f s E1 A + J/2 E2 X X X + J/2 X . Using the matrix elements of D(1) (see I. Therefore the carbon will be fast if it pairs with a spinup proton or slow if it pairs with a spindown proton.5.53) and (I.J/2 E3 E4 Figure I. according to (I. For carbon. those in states 3 and 4 are slow. a proton can add or subtract to the field "seen" by the carbon. i. The carbon spins will have a similar effect on protons. Figure I.22 Density Matrix Treatment Although they are indiscernible at thermal equilibrium. Fast and slow labeling. respectively. Those in states 2 and 4 are slow.
The chemical shift evolution Hte/2 is the average of the fast and slow evolutions discussed above [see (I. The longitudinal carbon magnetization changed sign: ( d11 d22 d33 d44 ) (3 2 3 2) 2 Figure I. As discussed above. is . Therefore inverting carbon orientation results in changing fast protons into slow protons and vice versa.25) and (I.26)]. We can verify that the matrix elements d*13 and d*24 are equal at t(4) [see (I. They have both precessed a total angle Hte from their starting position along y.23 24)]. This is mathematically documented in the DM treatment [see (I.14 16)] demonstrate the same thing: MTH ( MoH / 4 )( B * C *) ( MoH / 4 )[ 2 i exp( i 13te / 2 ) 2 i exp( i 24te / 2 )] i ( MoH / 4 ) exp( i H te / 2 )[exp( i Jte / 2 ) exp( i Jte / 2 )] The carbon is still not affected [Figure I. the real part represents vectors along the xaxis and the imaginary part vectors along the yaxis). The carbon magnetization was not affected [Figure I.2DHETCOR 23 This tells us that the pulse brought the proton magnetization on the yaxis (the reader is reminded that in the transverse magnetization.e..6b t(3) tells us that the 180xC pulse reverses the carbon magnetization and also reverses the proton labels. while 24 is lagging by the same angle (i. The fast vector 13 catches up with the slow 24 and at t(4) they coincide. It can be verified that the longitudinal proton magnetization is zero since d11 d22+d33 d44 = 2 2 3 3 0 (cf I. The matrix element B is transferred in the slow (24) "slot" and will evolve from now on with the slow frequency 24.6a t(2)]. MT = Mx + iMy. Figure I. The vector 13 is ahead by + Jte/2.53). the protons coupled to up carbons are fast and those coupled to down carbons are slow. The transverse magnetization.6b t(4) clearly shows that the second evolution te/2 completes the decoupling of proton from carbon. calculated from the matrix elements. Jte/2).6a t(1)]. The DM results [see (I.20)]. The reverse is happening to the matrix element C.
using (I. When we went through the DM treatment. for the comparison with the vector representation and for an understanding of the polarization transfer. its x components are not affected.53). Figure I. the vectors are now opposite. .33). It can be calculated by applying the rotation operator R90xH [see (I. with respect to the average. as expected after a 90x pulse.30)] that at t(5) the elements d13 and d24 are equal and of opposite signs.55) The magnetization components in Figure I.6b t(5) shows what happened during the delay 1 which has been chosen equal to 1/2J. As a result. Each of the two proton magnetization components rotated by an angle but. The result is D(6) 3 2s 0 2c 0 0 2c 2 2s 0 0 3 2s 2c 0 0 2c 0 2 2s (I. As far as the proton is concerned. after the 90xH pulse. while the other components rotate from y to z and from y to z.9)] to D(5) given in (I.6c shows the situation at t(6). What happens to the proton magnetization can be predicted from the previous vector representation but what happens to the carbon cannot. we combined the last two pulses into a single rotation operator and this brought us directly from D(5) to D(7). the fast component has gained /2 while the slow one has lost /2. The carbon magnetization did not change. it is necessary to discuss the density matrix D(6). We can verify [see (I. Figure I. The carbon magnetization is still along z. However.24 Density Matrix Treatment MTH ( MoH / 4 )[ 2 i exp( i H te ) 2 i exp( i H te )] iMoH exp( i H te ) After separating the real and imaginary parts in MTH we obtain MTH MxH MyH iMoH (cos H te i sin H te ) MoH (sin real part of MTH MoH sin H te coefficient of the imaginary part of MTH H te i cos H te ) H te MoH cos This is in full accordance with the vector representation.6c are derived from the matrix elements of D(6).
the quantity 2sMoC varies from +2MoC to 2MoC .95 The last pulse of the sequence. but it cannot explain the nulling of proton magnetization.6d t(7). a swing of 4MoC. Note that from t(5) on.57) (I. M12 becomes positive while M34 remains negative.e. brings us to D(7) [see (I.2DHETCOR 25 The net longitudinal carbon magnetization does not change. it is proton modulated.35)] and to Figure I. It is seen that the vector representation can explain how carbon magnetization is affected by the pulse (12 goes in y and 34 in +y).6c is drawn for s 0. it is still MoC . i. . In other words. The remaining of the sequence is designed to make this modulated term observable.58) MzC M12 M34 MoC The imbalance term is proportional to s = sin[ H(te+ 1)]. but a sizable imbalance is created between its fast and slow components: M12 ( MoC / 2 )( d11 d22 ) MoC ( 1 / 2 2 s ) M34 ( MoC / 2 )( d33 d44 ) MoC ( 1 / 2 2 s ) ( MoC / 2 )( 3 2 s 2 2 s ) ( MoC / 2 )( 3 2 s 2 2 s ) (I. The density matrix D(7) [see(I. My12 My34 MoC (1 / 2 2 s ) MoC (1 / 2 2 s ) The net carbon magnetization is MxC Mx12 Mx 34 0 .35)] shows MT12 MT 34 iMoC (1 / 2 iMoC (1 / 2 2s) 2s) Separation of the real and imaginary parts gives Mx12 Mx 34 0 0 . the fast carbons are now predominantly up and the slow ones predominantly down. a 90xC. The Figure I. A correlation has been created between the updown and the fastslow quality of the carbon spins. When s varies from +1 to 1.56) (I. the net magnetization was zero (opposite vectors) but now 13 and 24 are null themselves. For s greater than 1/4.
43) confirm that at time t(8) both matrix elements d*12 and d*34 have the same phase factor. . Nothing remarkable happens after the end of 2. We see in Figure I.26 Density Matrix Treatment MyC My12 My34 MoC The proton modulated term. This could not be even guessed from the vector representation.42) and (I. Relations (I. the two vectors (of unequal magnitude) are now coincident.6d t(8) that the two components have rotated by an average of C 2. The delay 2 will render it observable. exp(i C 2). This is the end of the vector representation of the 2DHETCOR sequence. is not yet observable (it does not appear in MxC or MyC). Such representation would not have been possible without the complete information provided by the DM treatment. As a result. 2s.59) The factor 4 in (I. The proton decoupler is turned on and the carbon magnetization is precessing as a whole during the detection time td (no spreadout of the fast and slow components).59) represents the enhancement of the carbon magnetization by polarization transfer. The net carbon magnetization is MTC * MoTC ( d12 * d34 ) C 2) MoC (1 / 2 2 s 1 / 2 2 s ) exp( i C 2) 4 sMoC exp( i (I. The fast one has gained /2 and the slow one has lost /2.
Actually the 1H magnetization at equilibrium is 16 times larger than that of 13C. . Vector representation of 2DHETCOR from t(0) to t(2).6a.2DHETCOR 27 H z C t(0) 12 34 y x Mz13= M = z24 Mo H 2 Mz12= M z34 = Mo C 2 t(1) 24 13 12 34 t(2) 24 Hte /2 Jte /2 12 34 13 Figure I. The magnetization vectors are arbitrarily taken equal for C and H in order to simplify the drawing.
.6b.28 Density Matrix Treatment H t(3) C 13 t e /2 H Jte / 2 24 12 34 t(4) H te 13 24 H 12 34 t(5) 13 H (t e + )1 24 12 34 Figure I. Vector representation of 2DHETCOR from t(3) to t(5).
. The carbon magnetization components depend on the value of s (they are proton modulated): (1 4 s ) MoC / 2 Mz12 (1 4 s ) MoC / 2 Mz 34 s sin H ( te 1) The figure is drawn for s 0.2DHETCOR 29 H C 12 13 t(6) 24 34 Figure I.6c.95. Vector representation of 2DHETCOR at time t(6).
. Vector representation of 2DHETCOR at t(7) and t(8).30 Density Matrix Treatment C t(7) 12 34 t(8) 12 34 Figure I.6d. both fast and slow. have vanished. The carbon magnetization components at t(7) are My12 (1 4 s ) MoC / 2 My34 (1 4 s ) MoC / 2 s sin H ( te 1) The proton magnetization components.
INADEQUATE
31
4. THE DENSITY MATRIX DESCRIPTION OF A DOUBLEQUANTUM COHERENCE EXPERIMENT (INADEQUATE)
The main goal of INADEQUATE (Incredible Natural Abundance DoublE QUAntum Transfer Experiment) is to eliminate the strong signal of noncoupled 13C nuclei in order to easily observe the 200 times weaker satellites due to CC coupling. This is realized by exploiting the different phase responses of the coupled and noncoupled spin signals when the phase of the observe pulse is varied (see Figure I.7). The receiver phase is matched with the desired signal. It shall be seen that the different phase behavior of the coupled nuclei is connected with their doublequantum coherence. The beauty of INADEQUATE resides in its basic simplicity: only a twostep cycle is theoretically needed to eliminate the unwanted signal. That the real life sequences may reach 128 or more steps is exclusively due to hardware (pulse) imperfections whose effects must be corrected by additional phase cycling. The essence of INADEQUATE can be understood by following the basic sequence shown in Figure I.7.
90x 180x 90x 90
td
t(0)
t(1) t(2)
t(3) t(4)
t(5)
t(6)
t(7)
t(8)
Figure I.7.
The INADEQUATE sequence: 90x (proton decoupling is
180x applied
90x 90 AT throughout the experiment).
32
Density Matrix Treatment
4.1 Equilibrium Populations
At thermal equilibrium the four energy levels shown in Figure I.8 are populated according to the Boltzmann distribution law, as shown in (I.1) through (I.5). In this case both A and X are 13C transition frequencies. The difference between A and X, due to different chemical shifts, is too small to be taken into account when calculating the populations. We assume q = p and (I.6) becomes:
P 1 P2 P3 P4
P 1 (1 p ) P 1 (1 p) P 1 (1 2 p) / P 1 PS 1
_____________________
1 (4 4 p ) P 1
Hence,
P 1/ S 1 P2 P3 (1 p) / S P4 (1 2 p) / S
where
S
4 4p
4
and the density matrix at equilibrium is:
P 1 D(0) 0 0 0
0 P2 0 0 1 1 0 4 0 0
0 0 P3 0 0 1 0 0
0 0 0 P4 0 0 1 0 1 4
1 0 0 0 0 p 0 4 0 0
0 1 p 0 0 0 1 0 0 0 0 1 0 0 0 0 2
0 0 1 p 0
0 0 0 1 2p
0 0 0 1
(I.60)
INADEQUATE
33
+1
(
) A + J/2
E1
A X X + J/2
0 0
( (
) ) X X  J/2
E2 E3
A A  J/2
1 m
(
)
E4 AX
Figure I.8. Energy levels of a homonuclear AX system (noncoupled and coupled). Transition frequencies and coupling constants are in Hz.
We will again ignore the (large) first term which is not affected by pulses or evolution, put aside the constant factor p/4 and start with
D(0)
0 0 0 0
0 1 0 0
0 0 1 0
0 0 0 2
(I.61)
In order to compare the results of the density matrix treatment with those of the vectorial representation, we will calculate for every step of the sequence the magnetization components, using the relations (B22). We must also consider that here q = p and that MoA (B15) = MoX = Mo/2, where Mo refers to magnetization due to adjacent 13C atoms A and X. Thus our magnetization equations become (cf. I.53):
M zA M zX
( M o / 4)(d11 d 22 d33 d 44 ) ( M o / 4)(d11 d33 d 22 d 44 )
* * ( M o / 2)(d12 d34 ) * * ( M o / 2)(d13 d 24 )
M TA M TX
(I.62)
34
Density Matrix Treatment
One can check that at thermal equilibrium, when D = D(0)
M zA M zX
( M o / 4)(0 1 1 2) M o / 2 ( M o / 4)(0 1 1 2) M o / 2
The transverse magnetization
M TA
4.2 The First Pulse
M TX
0
At time t(0) a nonselective pulse 90xAX is applied. Since all pulses in this sequence are nonselective, the notation AX will be omitted. The density matrix D(1) after the pulse is calculated according to:
D(0)
R 1 D(0) R
1
The rotation operator R and its reciprocal R pulse have been calculated in (I.34):
for the nonselective 90x
R
1 1 i 2 i 1
i 1 1 i
i 1 1 i
1 i i 1
;
R
1
1 1 i 2 i 1
i 1 1 i
i 1 1 i
1 i i 1
First we postmultiply D(0) by R:
D (0) R
0 i i 2
0 1 1 2i
0 1 1 2i
0 i i 2
what happens as we proceed. Let us see. 4. Considering that MT = Mx + iMy. though. Note that dmn(0) is the starting point of the evolution immediately after a given pulse.63) We note that the 90o pulse equalizes the populations and creates singlequantum coherences. The longitudinal magnetization is null while M TA ( M o / 2)(i /1 i / 2) iM o / 2 M TX MT ( M o / 2)(i /1 i / 2) M TA M TX iM o iM o / 2 We also note that the transverse magnetization is imaginary. If the evolution is described in a frame rotating at transmitter frequency tr equation (I.64) dmn is the matrix element and mn = (Em En)/ is the angular frequency of transition m n. So far. In our case the elements dmn(0) are those of D(1).INADEQUATE 35 Premultiplication with R 4 D (1) 1 2i 0 4 2i 2i 4 0 2i 2i 0 4 2i 1 leads to 0 2i 2i 4 2 1 i 2 i 0 i 2 0 i i 0 2 i 0 i i 2 (I. .3 Evolution from t (1) to t (2) The standard formula describing the (laboratory frame) time evolution of the density matrix elements in the absence of a pulse is: d mn (t ) d mn (0) exp( i mn t) (I.64) becomes: d mn (t ) d mn (0) exp( i mn t ) exp[i (mm mn ) tr t] (I.65) where mm and mn are the total magnetic quantum numbers of states m and n (see Appendix B). it follows that Mx = 0 and My = Mo. the vector representation would have been much simpler to use.
Hence. m4 = 1). The zeroquantum coherence matrix element is not affected by the rotating frame (m2 m3 = 0): d 23 (t ) d 23 (0) exp( i 23 t) d 23 (0) exp( i 23 t) (I. For instance d12 (2) d12 (1) exp( i 12 ) mn ( i / 2) exp( i ) 12 ) (I.and doublequantum coherences evolve at low frequencies in the rotating frame. For the doublequantum coherence matrix element d14 (t ) d14 (0) exp( i d14 (0) exp( i 14 14 t ) exp[i (1 1) t) tr t] (I. also. m2 = m3 = 0 . As expected.e. the diagonal elements are invariant during evolution since both exponentials are equal to 1.65) to our particular case (m1 = 1 .67) where 14 = 14 2 tr. i. the evoluition during the first delay .66) mn mn )t ] t) is the evolution frequency in the rotating frame.. d mn (t ) d mn (0) exp( i d mn (0) exp[ i ( d mn (0) exp( i where mn mn t ) exp(i tr tr t) (I. All single quantum coherences above diagonal have mm mn = 1.68) The zeroquantum coherence evolves at low frequency in both the laboratory and rotating frame. We note that both single. We now want to calculate D(2). because the detection is actually made at the resulting low (audio) frequencies.36 Density Matrix Treatment Let us apply (I.69) To save space we let ( i / 2) exp( i Bmn and at t(2) we have: 1 D (2) B * 12 * 13 B12 1 0 * B24 B13 0 1 * B34 0 B24 B34 1 (I.70) B 0 . The rotating frame treatment is useful not only for better visualization of the vector evolution but.
73) * B24 0 * B13 * B12 0 1 B12 (I. The transverse magnetization components are: M TA M TX * * ( M o / 2)( B12 B34 ) (iM o / 4)[exp(i 12 ) exp(i * * ( M o / 2)( B13 B24 ) (iM o / 4)[exp(i 13 ) exp(i 34 )] )] (I. First.72) 24 We see that there are four vectors rotating with four different angular velocities in the equatorial (xy) plane.71) (I.4 The Second Pulse The rotation operator for this pulse is 0 0 0 1 R180 yAX 0 0 1 At time t(3) the density matrix is: * B34 1 D (3) R 1 D (2) R B34 B24 0 1 0 B13 0 1 0 1 0 0 0 0 0 1 R180 yAX (I. We can identify (see Figure I.INADEQUATE 37 The zmagnetization is still zero (relaxation effects are neglected). all single quantum coherences were conjugated and changed sign.8): 12 34 13 24 12 A X X tr A J J J J 4. .74) 1 Two important changes have been induced by the 180o pulse.
coherences corresponding to fast precessing nuclei were transferred in "slots" corresponding to slow evolution. .5 Evolution from t (3) to t (4) According to (I. This means the vectors also changed labels.74).66) and (I. Second.77) d12 (4) Hence.75) 34 ) ] d13 (4) ( i / 2) exp( i 2 J ) d12 (4) U (I. due to the label change. 4.38 Density Matrix Treatment This means that all xcomponents changed sign while the ycomponents remained unchanged: MT * MT M x iM y M x iM y This shows.62) we calculate the corresponding magnetization vectors: M zA M TA M zX M TX 0 M o (U * V * ) iM o cos 2 J (I. indeed.79) We see that while the chemical shifts refocused the coupling continues to be expressed. the evolution during the second delay leads to * d12 (3) exp( i 12 ) B34 exp( i 12 ) ( i / 2) exp( i 34 ) exp( i 12 ) ( i / 2) exp[ i ( 12 ( i / 2) exp( i 2 J ) (I. that all four vectors rotated 180o around the yaxis.78) 0 Using (I. 1 D(4) U U * * U 1 0 V* U 0 1 V* 0 V V 1 (I.76) d 24 (4) d34 (4) ( i / 2) exp( i 2 J ) V (I.
INADEQUATE 39 4. this does not happen since all transverse components vanish. 4.6 The Third Pulse We apply to D(4) the same rotation operators we used for the first pulse and we obtain: D(5) 1 c 0 0 is 0 1 0 0 0 0 1 0 is 0 0 1 c (I. evolves accord D(6) 1 c 0 0 w* 0 1 0 0 0 0 1 0 w 0 0 1 c (I. D(5) tells us that all singlequantum coherences vanished.78)] we had magnetization components on both x and y axes.7 Evolution from t (5) to t (6) The doublequantum coherence element. a doublequantum coherence was created and the only existing magnetization is along the zaxis. since U and V are complex quantities.67): is. In reality. Our interest is in the doublequantum coherence w. Turning to vector representation.81) where w = isexp( i 14 ) = isin2 J exp( i 14 ). In order to maximize it. we select = (2k+1)/4J where k = integer. as seen from the DM treatment. The vector description would indicate that the 90x pulse leaves the x components unchanged. ing to (I.80) where c = cos2 J and s = sin2 J . it is seen that before the pulse [see(I. Then c = 0 and s = sin[(2k+1) /2] = 1 = (1)k .
82) where w i ( 1)k exp( i 14 ) The last expression of D(6) tells us that at this stage there is no magnetization at all in any of the three axes. 1 R90 AX a 1 1 a* a 1 1 a* a2 a a 1 (I.82)] the populations are equalized and all information is contained in the w elements. This would be impossible to derive from the vector representation. For clarity we will discuss the coupled and the noncoupled (isolated) carbon situations separately. the pulse is applied on axis x. D(6) 1 0 0 w* 0 1 0 0 0 0 1 0 w 0 0 1 (I. respectively. The general various combinations along the x. 4. . or y. y. In the first case (coupled 13C spins).83) 1 2 a* a* a *2 where a = iexp( i ) and is the angle between the xaxis and the direction of B1.. y. we observe that at t(6) [see(I. and y axes. When takes the value 0. 180o or 270o. i. expression of the 90 AX operator is given in Appendix C [see(C39)].8 The Fourth Pulse This pulse is phase cycled. which also could not explain the reapparition of the observable magnetization components after the fourth pulse. it is applied successively in x.e. x.40 Density Matrix Treatment With this value of . 90o.
the density matrix would allow the reader to draw the corresponding vectors. We can use (I. 14. w = 0) : D '(6) 2 0 0 0 0 1 0 0 0 0 1 0 0 0 0 0 0 a/2 a/2 1 (I.81) letting J = 0 (c = 1.86) In this case D(7) becomes D '(7) a/2 a/2 1 a*/ 2 1 0 a*/ 2 0 1 a*/ 2 a*/ 2 0 (I.85) D(7) shows that the newly created single quantum coherences contain the double quantum coherence information. The transverse magnetization is zero (fast and slow vectors are equal and opposite). s = 0.84) where (I. To save time and space we will treat the isolated (uncoupled) carbons as an AX system in which A and X belong to two different molecules.INADEQUATE 41 The result of R901 AX D(6) R90 AX is: D(7) 1 a2 F a *G a *G F 1 a2 F aG a2 F a *G 2 2 aG a F 1 a F a *G F aG aG 1 a 2 F F G ( w w*) / 4 ( w w*) / 4 (1/ 2)( 1) k sin (1/ 2)( 1)k cos 14 14 (I.87) D'(7) shows only single quantum coherences and equalized populations. None of these could be deduced from the vector representation. Yet. A longitudinal magnetization proportional to sin 14 appears. . The transverse magnetization of the noncoupled spins is equal to their equilibrium magnetization M'o (its orientation depends on the value of ).
The table below shows that two cycles are sufficient to eliminate MT(ncpl).) 1 1 2 Even small imperfections of the rf pulse will allow leakage of the strong undesired signal into the resultant spectrum.9 Detection The magnetization at t(8). We note that MT(cpl) and MT(ncpl) depend in opposite ways on since one contains a and the other a* [cf.84) and (I.42 Density Matrix Treatment 4. For the noncoupled carbons M T (ncpl ) where M '[2 exp(i A d t ) 2 exp(i X d t )] (I.89)]. Each of them is 200 times more intense than each of the four peaks in (I.(I. Cycle 1 2 (1+2) 0 90o 0 90o ncpl expi( .88) M M o aG* ( M 0 / 2) exp( i )( 1) cos These are the four peaks of the coupled AX system shown as a schematic contour plot in Figure I.88).9.87) respectively.. They can be discriminated by cycling choosing the receiver phase [the detected signal S = MT exp(i )]. M T (cpl ) where M [exp(i exp(i t ) exp(i exp(i 24t d ) 12 d 13 d t ) 34 td )] k 14 (I. This makes it necessary to apply one of several cycling patterns consisting of up to .89) M' ' ' M o a * / 2 ( iM o / 2) exp( i ) These are the two peaks of the uncoupled nuclei. The culminating point of INADEQUATE is the selective detection of MT(cpl).) 1 1 0 cpl expi(.88) and properly and (I. due to coupled (cpl) and noncoupled (ncpl) nuclei can be calculated starting from the single quantum coherences in (I.
13 C atoms. All we have to do now is to discuss (I. As seen in Figure I. 4.9. The four peaks due to a pair of coupled vertical scale is twice larger than the horizontal scale. The great advantage of the 2D display consists of the fact that every pair of coupled carbons will exhibit its pair of doublets along its own 14 frequency. too short.89) in terms of two time variables. The .9. pulses. all four peaks of MT(cpl) will be aligned in domain along the same frequency 14 = A + X. or incorrectly phased. which attempt to cancel the effects of too long.INADEQUATE 43 256 steps. This allows us to trace out the carbon skeleton of an organic molecule.88) and (I.10 CarbonCarbon Connectivity A significant extension of INADEQUATE is its adaptation for twodimensional experiments. The second timedomain (in addition to td) is created by making variable. 0 A X d 14 Figure I.
when incompletely eliminated. mirrorimage peaks will appear at frequencies 14. The answer is in the footnote on page 59. It should be noted that MT(ncpl) does not depend on [cf.(I. the analog of a quadrature detection in domain .0 12. We also note that MT(cpl) is phase modulated with respect to td and amplitude modulated with respect to . A modified sequence has been proposed to obtain phase modulation with respect to . This means that.1 34.1 ppm Figure I. ~ ~ ~ ~ 53.10. increasing the size of the data matrix. the peaks of isolated carbons will be "axial" (dotted circles on the zero frequency line of domain ). Consequently.2 26.81)]. . The carboncarbon connectivity spectrum of a molecule with MW = 137.10 and to determine its carboncarbon connectivities.44 Density Matrix Treatment The student is invited to identify the molecule whose 2D spectrum is shown in Figure I. This reduces the intensity of the displayed signals and imposes restrictions on the choice of the transmitter frequency.
the populations at thermal equilibrium follow a pattern identical to that of INADEQUATE (see I.11.1 Equilibrium Populations Since we deal with a homonuclear AX system. 90x te td 90x t(0) t(1) t(2) t(3) t(4) Figure I. Of course. The initial density matrix is: D(0) 0 0 0 0 0 1 0 0 0 0 1 0 0 0 0 2 (I. other spin 1/2 systems such as 19F can be successfully studied with this 2D sequence.11.90) .61). The basic sequence is shown in Figure I. The Basic COSY sequence (without phase cycling): 90x te 90x AT 5. particularly for disentangling complicated proton spectra by protonproton chemical shift correlation and elucidation of the coupling pattern.COSY 45 5.60 and I. DENSITY MATRIX DESCRIPTION OF COSY (HOMONUCLEAR CORRELATION SPECTROSCOPY) COSY (COrrelation SpectroscopY) is widely used.
The singlequantum coherences will evolve.2 The First Pulse Here. also.63) since the first pulse is a nonselective 90xAX: D (1) 2 1 i 2 i 0 i 2 0 i i 0 2 i 0 i i 2 (I. we use the rotation operators for the 90xAX pulse given in (I.34) R 1 1 i 2 i 1 i 1 1 i i 1 1 i 1 i i 1 .3 Evolution from t (1) to t (2) Only nondiagonal terms are affected by evolution. R 1 1 1 i 2 i 1 i 1 1 i i 1 1 i 1 i i 1 . we can use the results from INADEQUATE (I.91) 5. each with its own angular frequency. leading to: D(2) A B 0 1 A* 1 0 C 1 D B* 0 0 C * D* 1 A i / 2 exp i / 2 exp i / 2 exp i / 2 exp i i i i 12 e 13 e 24 e 34 e (I.93) t 5.46 Density Matrix Treatment 5.92) t where B C D t t (I.4 The Second Pulse To calculate D (3) R 1 D (2) R .
COSY 47 The postmultiplication D(2)R yields 1 2 1 iA iB i A* C i B* D 1 iC * iD * A B 1 iA * iC 1 iB * iD i C* D* 1 i i A B 1 iA * iC 1 iB * iD i C* D* and obtain 1 iA iB i A* C i B* D 1 iC * iD * We then premultiply this result by R D (3) 4 iA iA * iB iB * iC iC * iD iD * A A* B B* C C* D D* R 1 D (2) R A A* B B* C C* D D* iA iA * iB iB * iC iC * iD iD * A A* B B* C C* D D* 1 4 A A* B B* C C* D D* iA iA * iB iB * iC iC * iD iD * 4 iA iA * iB iB * iC iC * iD iD * iA iA * iB iB * iC iC * iD iD * A A* B B* C C* D D* iA iA * iB iB * iC iC * iD iD * 4 iA iA * iB iB * iC iC * iD iD * A A* B B* C C* D D* A A* B B* C C* D D* A A* B B* C C* D D* 4 iA iA * iB iB * iC iC * iD iD * (I.94) .
are all real quantities. etc. are imaginary.e. i. C C* s34 . D D* With the new sine/cosine notations. it has the same value for D(0) through D(3). Also. This can be used to simplify the expression of D(3) by employing the following notations: A ( i / 2) exp i 12 e t ( i / 2) cos 12 e t i sin 12 e t A* A B C D ( i / 2)(c12 is12 ) (1/ 2)( s12 ic12 ) 1 2 s12 ic12 1 2 s13 ic13 (1/ 2)( s12 ic12 ) With similar notations for B. B B* s12 . while the differences A A * .95) ic34 1 2 s24 ic24 ....96) is12 is24 is13 is34 ic12 s24 s13 ic34 s12 ic24 ic13 s34 4 c12 c24 c13 c34 . and D we obtain: . D(3) becomes: 4 c12 c24 s12 ic24 1 4 ic12 s24 s13 ic34 is12 is24 is13 is34 4 c12 c24 c13 c34 s12 ic24 ic13 s34 c13 c34 ic13 s34 s12 ic24 4 c12 c24 ic13 s34 c13 c34 ic12 s24 is12 is24 s13 ic34 is13 is34 is12 is24 ic12 s24 is13 is34 s13 ic34 (I. B B * . etc. A A* . C. B B* s24 . In doing this verification we keep in mind that the sums A A * . D D* ic12 ic13 ic24 (I. D(3) is Hermitian (the density matrix always is). B B * . C C* 1 2 s34 ic34 .48 Density Matrix Treatment One can check that the population sum d11 d 22 d33 d 44 (trace of the matrix) is invariant. A A* s13 .
97) Their complex conjugates. 13te . and d24 in the time domain td. which are needed for the calculation of magnetization components. d13..e. d34.98) d (3) d (3) d (3) * 24 * 13 * 34 Each of the four matrix elements above contains all four frequencies evolving in domain te. Before evolution they are (from I. each of them will evolve with its own frequency in the domain td : * d12 (4) * d34 (4) * d13 (4) * d 24 (4) i 4 i 4 i 4 i 4 is12 is34 c13 c24 exp i is12 is34 c13 c24 exp i c12 c34 is13 is24 exp i c12 c34 is13 is24 exp i 12 d 34 d 13 d 24 d t t t (I.5 Detection Since no other pulse follows after t(3) we will consider only the evolution of the observable (single quantum) elements d12. Thus.99) shows that each td frequency is modulated by all four te frequencies. are: * d12 (3) i 4 i 4 i 4 i 4 is12 is34 c13 c24 is12 is34 c13 c24 c12 c34 is13 is24 c12 c34 is13 is24 (I. Actually. while the te domain is amplitude modulated (i. there will be 32 peaks.96): d12 (3) d34 (3) d13 (3) d 24 (3) i 4 i 4 i 4 i 4 is12 is34 c13 c24 is12 is34 c13 c24 c12 c34 is13 is24 c12 c34 is13 is24 (I. because only the td domain is phase modulated.COSY 49 5. we expect sixteen peaks in the 2D plot. 34 te . . namely: 12 te . it contains sine/cosine expressions). During detection. and 24 te .99) t Expression (I.
Contour plot of COSY without phase cycling. e 13 24 12 34 34 34 12 12 24 13 d 24 13 Figure I.12. The transmitter frequency is on one side of the spectrum.50 Density Matrix Treatment Each sine or cosine implies both the positive and the negative frequency according to c jk is jk cos i sin jk e t jk e t 1 exp i 2 1 exp i 2 jk e t exp exp i i jk e t jk e t jk e t This leads to the 32 peak contour plot in Figure I. .12.
. The 12 next section shows how this can be circumvented by means of an appropriate phase cycling.13. e 13 24 34 12 12 34 24 13 34 12 24 13 d Figure I. If the transmitter is placed within the spectrum (e. between and 24).. If the transmitter is placed within the spectrum.13.g. a messy pattern is obtained as shown in Figure I.. The spectral widths have to be doubled and the data matrix increases by a factor of four. it causes overlap of positive and negative frequencies. we lose the advantage of quadrature detection in both domains). Contour plot of COSY without phase cycling.COSY 51 We can plot the positive frequencies only.e. but the amplitude modulation in domain te still is a major drawback since it requires placing the transmitter frequency outside the spectrum (i.
52 Density Matrix Treatment 6.15 have a common segment [t(0) to t(2)].14 differs from that discussed above (Figure I. Rather than doing the density matrix calculations for an arbitrary phase . only two steps are theoretically necessary to eliminate negative frequencies in domain te. we can take D(2) from the previous section [see (I. we will take advantage of the fact that we have already treated the x phase in the previous section.1 Comparison with the Previous Sequence The sequence for COSY with phase cycling shown in Figure I. The second pulse is successively phased in x and y.11) only by the cycling of the second pulse.11 and I.93)].15). D (2) A B 0 1 A* 1 0 C 1 D B* 0 0 C* D* 1 (I. COSY WITH PHASE CYCLING 6. 90x 90 te td t(0) t(1) t(2) t(3) t(4) Figure I. Since the two sequences in Figures I.14.100) .92). and (I. COSY sequence with phase cycling of second pulse: 90x te 90 AT Moreover. Only the effect of 90yAX must then be calculated (see Figure I.
101) 1 1 R 1 1 1 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 . These operators are (see Appendix C): R90 yA 1 1 1 2 0 0 1 1 0 0 0 0 1 1 0 0 1 1 . is shown below together 1 1 1 2 1 1 1 1 1 1 1 1 1 1 1 1 (I.15. R90 yAX .2 The Second Pulse The rotation operator for the 90yAX pulse can be obtained by multiplying R90yA by R90yX. R 1 . R 1 . R90 yX 1 1 0 2 1 0 0 1 0 1 1 0 1 0 0 1 0 1 The result of the multiplication.COSY 53 90x 90y te td t(0) t(1) t(2) t(3) t(4) Figure I. R with its reciprocal. The second step of the phase cycled COSY sequence: 90x te 90y AT 6.
54 Density Matrix Treatment The postmultiplication D(2)R yields 1 A B 1 A* C 1 2 1 B* D 1 C * D* 1 1 1 1 A B A* C B* D C* D* 1 1 1 1 1 A B A* C B* D C * D* 1 A 1 A* i B* 1 C* B C D D* Premultiplying this result by R gives D(3) 4 A A* B B* C C* D D* A B C D 1 4 A B C D A* B* C* D* A* B* C* D* A B C D A* B* C* D* R 1 D(2) R A B C D A B C D A* B* C* D* A* B* C* D* A B C D A B C D A B C D A* B* C* D* A* B* C* D* A* B* C* D* 4 A A* B B* C C* D D* A B C D A* B* C* D* 4 A A* B B* C C* D D* A B C D A* B* C* D* A B C D A* B* C* D* A B C D A* B* C* D* 4 A A* B B* C C* D D* (I.102) .
C C* 1 2 s34 ic34 .105) . C C* s34 .103) ic34 1 2 s24 ic24 . A A* s13 . B B* s12 .COSY 55 With the same notations as in (I.95) : A B C D 1 2 s12 ic12 1 2 s13 ic13 .104) ic12 ic24 ic13 ic34 s12 ic24 ic13 s34 ic12 s24 s13 ic34 4 s12 s24 s13 s34 We have to consider only the observable matrix elements : d12 (3) d34 (3) d13 (3) d 24 (3) i 4 i 4 i 4 i 4 c12 c34 is13 is24 c12 c34 is13 is24 is12 is34 c13 c24 is12 is34 c13 c24 (I. D D* D(3) becomes 4 s12 s24 ic12 s24 s13 s34 s13 ic34 ic13 s34 ic12 s24 s13 ic34 s13 s34 ic13 ic34 s12 ic24 ic12 ic24 ic13 s34 ic13 ic34 s13 s34 ic12 ic24 s12 ic24 ic12 s24 ic13 ic34 ic13 s34 s13 ic34 4 s12 s24 ic12 ic24 1 4 s12 ic24 4 s12 s24 (I. A A* . B B* s24 . D D* ic12 ic13 ic24 (I.
This will lead to the desired phase modulation.106) The complex conjugates of the matrix elements above (needed for the expression of the magnetization components) are * d12 (3) * d34 (3) * d13 (3) * d 24 (3) i 4 i 4 i 4 i 4 is12 c12 ) (is34 c34 ) ( c13 is13 ) (c24 is24 is12 c12 ) (is34 c34 ) (c13 is13 ) ( c24 is24 c12 is12 ) (c34 is34 ) (is13 c13 ) (is24 c24 c12 is12 ) ( c34 is34 ) (is13 c13 ) (is24 c24 (I. therefore we can use the notation e jk c jk is jk exp i jk te (I.97) shows that c and is are interchanged in all terms.108) With this notation (I.105) with those for phase x (I.107) We observe that every parenthesis represents an exponential. Addition of (I.56 Density Matrix Treatment Comparing the results for phase y (I.107) becomes * d12 (3) * d34 (3) * d13 (3) * d 24 (3) i 4 i 4 i 4 i 4 e12 e34 e13 e24 e12 e34 e13 e24 e12 e34 e13 e24 e12 e34 e13 e24 (I.109) .105) gives d12 (3) d34 (3) d13 (3) d 24 (3) i 4 i 4 i 4 i 4 is12 c12 ) (is34 c34 ) (c13 is13 ) ( c24 is24 is12 c12 ) (is34 c34 ) ( c13 is13 ) (c24 is24 c12 is12 ) ( c34 is34 ) (is13 c13 ) (is24 c24 c12 is12 ) (c34 is34 ) (is13 c13 ) (is24 c24 (I.97) and (I.
There are four diagonal terms. Instead of sines or cosines. The above discussion . four times larger. In other words we have achieved phase modulation in the domain te. The diagonal and neardiagonal peaks of nucleus A are all positive and they collapse into one diagonal peak. each having the same frequency in both domains te and td. If the two frequencies differ only by J (e. Two noncoupled spins will exhibit only diagonal peaks. likewise 13 = 24 = X. * d12 (4) * d34 (4) * d13 (4) * d 24 (4) i 4 i 4 i 4 i 4 e12 e34 e13 e24 exp i e12 e34 e13 e24 exp i e12 e34 e13 e24 exp i e12 e34 e13 e24 exp i 12 d 34 d 13 d 24 d t t t (I.110) t The expressions (I.g. both on the diagonal. The offdiagonal peaks come in groups of four. they contain only exponentials. with frequencies A and X. we have 12 in domain te and 34 in domain td) we have a "neardiagonal" peak. The remaining eight are referred to as offdiagonal or crosspeaks and their presence indicates that spins A and X are coupled. This pattern is no longer dependent on the position of the transmitter since we have achieved the equivalent of quadrature detection in both domains. The same is true for nucleus X. two positive and two negative.110) correspond to a contour plot with 16 peaks.16 collapses into a single peak in the center of the corresponding square.3 Detection The evolution during td is identical for the two acquisitions. therefore we can apply it after the summation (in I.COSY 57 The reader is reminded that the above expressions represent the summation from two acquisitions. When they collapse (J=0) they cancel each other and there will be no offdiagonal peak.109). There are four such peaks. In this case 12 = 34 = A (center of the doublet). one with phase x and the other with phase y for the second pulse. We can verify that this is so by discussing what happens if J becomes vanishingly small. as represented in Figure I. Therefore each group of 4 peaks in Figure I. The net result is a spectrum with just two peaks.. 6.16.
to avoid phasing problems. Open circles are positive peaks. Contour plot of COSY with phase cycling.16. While it is well known that this procedure helps canceling out radiofrequency interferences and pulse imperfections. The MC is applied to this signal and it cannot represent the original amplitude of the two peaks. one positive and one negative. we have just seen that it can be . will both become positive in MC. The magnitude calculation (the absolute value of a complex quantity) is performed by the computer after Fourier transform in both domains. provided they are well resolved. Therefore the use of magnitude calculation does not provide a solution for poorly resolved multiplets. Two peaks. One word about the utility of phase cycling. shaded circles are negative peaks. If they are illresolved. they will cancel each other partially and will yield a much smaller signal. It is common practice to plot the 2D spectra in the "magnitude calculation" (MC) or "absolute value" mode. There is one more observation. e 13 24 12 34 34 12 24 13 d Figure I.58 Density Matrix Treatment shows that COSY is not suited for spectra with illresolved multiplets because there will be destructive overlap in the offdiagonal groups.
________________________________________________________ Answer to the problem on page 44: The contour plot in Figure I. However. to efficiently compensate for hardware imperfections. The limitation of this approach is the rapidly increasing volume of calculation with increasing number of nuclei. In COSY it helps achieve phase modulation in domain te. The size of the matrix goes from 16 elements for a two spin 1/2 system to 64 and 256 elements for three and four spin systems. 7. CONCLUSION OF PART I The density matrix approach described above constitutes a very clear and useful means for understanding the multipulse sequences of modern NMR. We must therefore resort to an avenue which affords a "shorthand" for the description of rotations and evolutions.COSY 59 useful for other purposes.10 is the carboncarbon connectivity spectrum of 2bromobutane. The new avenue we present in the second part of this monograph is the product operator formalism. . respectively. In INADEQUATE it helps eliminate the NMR signal from the 13C12C pairs while preserving that from 13C13C pairs. In both cases a two step cycling is theoretically sufficient. cycling in more than two steps is generally employed.
35)]: 60 . We will thus introduce a "basis set" which is composed of "product operators. in order to express evolutions of coupled spins. Moreover. However.Iz). 1 + p and 1 + q. 2. respectively [see (I. beginning with 2DHETCOR. effects of pulses (rotations) and evolutions of noncoupled spins can also be described in terms of angular momentum components (Ix. We will describe this approach and will apply it to several pulse sequences.Iy. EXPRESSING THE DENSITY MATRIX IN TERMS OF ANGULAR MOMENTUM COMPONENTS We start with the same procedure of describing the density matrix at equilibrium. In order to generalize the approach to an AX (not only a CH) system we preserve separate Boltzman factors." The latter are either products between angular momentum components or products of angular momentum components with the unit matrix. for nuclei A and X. as in Part I.2 The Product Operator Formalism 1. INTRODUCTION In this section we will see that the density matrix at equilibrium can be expressed in terms of the spin angular momentum component Iz of each nucleus. D(0). we will need additional "building blocks" besides angular momentum components.
The PO Formalism
61
D(0)
1 N
1 0 0 0
0 1 p 0 0
0 0 1 q 0
0 0 0 1 p q
(II.1)
N is the number of states (4 for an AX system). As we did in Part I, we separate the unit matrix from the matrix representing population differences. However, here we choose as a factor for the unit matrix the average population (1+p/2+q/2)/N:
1 0 0 0
D(0)
1 p/2 q/2 0 1 0 0 0 0 1 0 N
0 0 0 1
1 N
p/2 q/2 0
0
p/2 q/2
0 0
0 0
0 0 p/2 q/2 0
0 0 0
p/2 q/2
(II.2)
Again, we ignore the term containing the unit matrix which does not contribute to magnetization.
D(0)
1 N
p/2 q/2 0 0 0
0 p/2 q/2 0 0
0 0 p/2 q/2 0
0 0 0 p/2 q/2
(II.3)
62
Product Operator Treatment
Separation of the p and q terms gives
D(0)
1 p 0 2N 0 0
0 1 0 0
0 0 1 0
0 0 0 1
1 q 0 2N 0 0
0 1 0 0
0 0 1 0
0 0 0 1
(II.4)
We recognize in the first term the angular momentum component IzA and, in the second term, IzX [see (C13) and (C15)]. We note that the signs of the magnetic quantum numbers are in the same order as in Figure I.1 of Part I. We can now write D(0) in shorthand:
D (0)
p I zA N
q I zX N
(II.5)
3. DESCRIBING THE EFFECT OF A PULSE IN TERMS OF ANGULAR MOMENTA
The rotation operator for a 90o pulse along the xaxis on nucleus X is:
R90 xX
1 0 i 0 1 0 1 0 i 2 i 0 1 0 0 i 0 1
(see I.9)
Its reciprocal is:
R901xX
1 1 0 2 i 0
0 1 0 i
i 0 1 0
0 i 0 1
(see I.10)
The PO Formalism
63
We postmultiply D(0) from (II.3) with R90xX (R, for brevity).
D(0) R
1 2N
p q 0 0 0 p q 0 ip iq 0
0 p q 0 0 0 p q 0 ip iq
0 0 p q 0 ip iq 0 p q 0
0 0 0 p q 0 ip iq 0 p q
1 0 i 0 1 0 1 0 i 2 i 0 1 0 0 i 0 1
1 2 2N
(II.6)
We now premultiply this result by R1 D(1) = R1[D(0) R]
1 1 0 4N i 0
2p 0 2iq 0
0 1 0 i
i 0 1 0
0 2p 0 2iq
0 i 0 1
2iq 0 2p 0
p q 0 ip iq 0
0 2iq 0 2p
0 p q 0 ip iq
p 0 iq 0
ip iq 0 p q 0
0 p 0 iq iq 0 p 0
0 ip iq 0 p q
0 iq (II.7) 0 p
1 4N
1 2N
Separation of p and q yields
D(1)
1 p 0 2N 0 0
0 1 0 0
0 0 1 0
0 0 0 1
0 q 0 2N i 0
0 0 0 i
i 0 0 0
0 i 0 0
(II.8)
64
Product Operator Treatment
Comparing the result with (C13) and (C14) we recognize IzA and IyX and we can write
D(1)
p I zA N
q I yX N
(II.9)
Relations (II.5) and (II.9) open the way toward the product operator formalism. We succeeded in writing D(0) and D(1) in angular momentum shorthand. Moreover, we foresee the possibility of obtaining the result of pulses without matrix calculations; this can be seen by simply representing the angular momenta in their vector form, as in Figure II.1.
z
z
y
90xX (q/N)I yX
y
(p/N)IzA
x x
(p/N)IzA
(q/N)IzX
( p / N ) I zA (q / N ) I zX
90 xX
( p / N ) I zA (q / N ) I yX
Figure II.1. Effect of the 90xX pulse.
We note that, because of our convention to take gamma as negative (see Appendix J) the angular momentum vector orientation is opposite to that of the magnetization vector which was used in Part I.
7) gives: D(2) p 0 p 1 0 2N F * 0 0 G* F G F 0 p 0 0 G 0 p 13 e (II. Applying (I. Now the exponentials in (II.13) to D(1) in (II.11) can be written as: exp( i exp( i 13 e t / 2) (c is)(C iS ) (c is)(C iS ) 24te / 2) (II.The PO Formalism 65 4.15) .12) the exponentials in (II. c and s (lower case) represent effects of chemical shift and C and S (upper case) represent effects of Jcoupling.10) where iq exp( i iq exp( i 13 24 t / 2) 24 te / 2) J J (II.11) become exp( i t / 2) exp[ exp( exp( i 24te / 2) exp[ exp( 13 e i( X J )te / 2] i X te / 2) exp( i Jte / 2) i( X J )te / 2] i X te / 2) exp( i Jte / 2) s sin X te / 2 S sin Jte / 2 (II.14) Note that here c and s have different meanings than the ones assigned in Part I (I.13) We make now the following notations: c cos X te / 2 C cos Jte / 2 (II.11) With the notations X X (II. To make sure. AN UNSUCCESSFUL ATTEMPT TO DESCRIBE A COUPLED EVOLUTION IN TERMS OF ANGULAR MOMENTA Let us calculate the result of a coupled evolution of duration te/2 starting from D(1).31).
qsC. and qcS: D(2) 1 p 0 2N 0 0 0 0 q sS i 2N 0 0 1 0 0 0 0 0 i 0 0 1 0 i 0 0 0 0 0 0 1 0 i 0 0 0 0 0 1 0 0 q cC i 2N 0 0 0 q sC 1 2N 0 1 0 0 0 0 1 0 0 0 0 0 i 0 0 0 1 i 0 0 0 1 0 0 0 0 1 0 0 0 i 0 0 0 0 q cS 1 2N 0 (II. qcC.18) . qsS.17) We separate D(2) into five matrices containing the factors p.16) iq (cC sS ) q( sC cS ) 0 p 0 and we can rewrite D(2) as p 0 0 p 0 iq (cC sS ) q( sC cS ) 0 iq(cC sS ) q ( sC cS ) 0 p 1 2 N iq(cC sS ) q( sC cS ) 0 (II.66 Product Operator Treatment Then F and G become F G iq(c is)(C iS ) iq(c is )(C iS ) iq(cC sS ) q ( sC cS ) iq(cC sS ) q ( sC cS ) (II.
Table II. second.(C12C15)]. This shows that the six angular momentum components shown in parenthesis are not sufficient to express the density matrix after a coupled evolution. IyA. For a given castle the child may not need to use all the building blocks. The first term is (p/N)IzA. and fourth. IxX. contain angular momenta [cf. IyX. but he knows that none of the castles would require a block he does not have. IzA.1 a complete set of such operators for the AX system. The bracket notations proposed by us will be defined as we explain how this set was put together.1 Basis Operators for 2 Nuclei (I = 1/2) [11] 1 0 0 0 1 0 0 0 0 1 0 0 0 1 0 0 0 0 1 0 0 0 1 0 0 0 0 1 0 0 0 1 [ z1] 1 0 0 0 1 0 0 0 0 1 0 0 0 1 0 0 0 0 1 0 0 0 1 0 0 0 0 1 0 0 0 1 [1z ] [ zz ] . We may use as an analogy the blocks a child would need to build any number of castles of different shapes given in a catalog.18) contain neither angular momenta nor a linear combination of the six components (IxA. IzX) known to us. The third and fifth matrices in (II. the first. PRODUCT OPERATORS (PO) We will call each building block a basis operator and will give in Table II. We will see in the next section how we can put together a complete (basis) set which will allow us to treat coupled evolutions in a shorthand similar to that used for D(0) and D(1). the second is (q/N)cCIyX and the fourth is (q/N)sCIxX.The PO Formalism 67 In (II. 5.18) only three terms. In other words they constitute an incomplete set of operators.
Bodenhausen. 16.Sörensen.R.H. and . G.68 Product Operator Treatment [ x1] 0 1 0 0 0 1 0 0 0 0 1 0 1 0 0 0 1 0 0 0 0 0 0 1 0 0 0 1 0 0 0 1 1 0 0 0 0 0 1 0 0 0 1 0 0 1 0 0 [ y1] 0 i 0 0 0 i 0 0 0 0 i 0 i 0 0 0 i 0 0 0 0 0 0 i 0 0 0 i 0 0 0 i i 0 0 0 0 0 i 0 0 0 i 0 0 i 0 0 [ xz ] [ yz ] [1x] [1 y ] [ zx] 0 0 1 0 0 0 0 1 0 0 0 1 0 0 1 0 1 0 0 0 0 1 0 0 0 1 0 0 1 0 0 0 [ zy ] 0 0 i 0 0 0 0 i 0 0 0 i 0 0 i 0 i 0 0 0 0 i 0 0 0 i 0 0 i 0 0 0 [ xx] [ xy ] [ yx] 0 0 0 i 0 0 i 0 0 i 0 0 i 0 0 0 [ yy ] 0 0 0 1 0 0 1 0 0 1 0 0 1 0 0 0 These product operators have been introduced by Ernst and coworkers (see O.Eich. and R.Ernst in Progress in NMR Spectroscopy.Levitt.W. G. M. 1983. 163192.W.
2IzX. Thus. Proof: 1 0 0 0 0 1 0 0 0 0 1 0 0 0 0 1 1 0 0 0 0 1 0 0 0 0 1 0 0 0 0 1 1 0 0 0 0 1 0 0 0 0 1 0 0 0 0 1 2 I zA Another example: 2 I zX [ zz ] (II.20) The basis set in Table II. Each basis operator is a product of two factors.21) If we were to continue now to transform into product operators (PO) all the subsequent density matrices of HETCOR we would. of course.19) [ x1] 2 I xA 1 2 I xA 0 1 0 0 1 0 0 0 0 0 0 1 0 0 1 0 (II. For example in the product operator [zz] the first factor is 2IzA and the second. 2Iz) or the unit matrix. The real advantage will consist in finding a way to go from one PO to the next PO .18) contains the product operator [zy] and the fifth term contains [zx].1 allows us now to write (II. one for each of the two nuclei (hence. the name "product operator"). 2Iy. The factor corresponding to a given nucleus may be one of its own angular momentum components multiplied by two (2Ix. but this would do us no good. D (2) ( p 2 N )[ z1] (q / 2 N )cC[1 y ] (q / 2 N ) sS [ zy ] (q / 2 N ) sC[1x] (q / 2 N )cS[ zx] (II.18) in shorthand because we recognize that the third term in (II. The operators we use are multiplied by a factor of 2 in order to avoid writing 1/2 so many times. be able to do it.The PO Formalism 69 references cited therein).
.y. PULSE EFFECTS (ROTATIONS) IN THE PRODUCT OPERATOR FORMALISM The great advantage of expressing the density matrix in terms of product operators is found in the dramatic simplification of calculations needed to describe pulse effects (rotations). Indeed. There is a small price to pay for this advantage. (2) 90xA pulse applied to D(0): 90 xA ( p / 2 N )[ z1] (q / 2 N )[1z ] D(0) ( p / 2 N )[ y1] (q / 2 N )[1z ] D(1) By following the same procedure in examples 3 to 5 we find out that the product operators after any rotation can be written by changing the labels x. Let us illustrate this by a few examples. namely learning a few rules which show how to obtain a new PO representation after pulses or evolutions. It will be seen later that the PO advantage is much more important when we have to handle systems of more than two spins.70 Product Operator Treatment without using matrices.z. of the affected nucleus according to the rotation which took place in the vector representation. (1) 90xX pulse applied to D(0): 90 xX ( p / 2 N )[ z1] (q / 2 N )[1z ] D(0) ( p / 2 N )[ z1] (q / 2 N )[1y ] D(1) This PO operation can be readily visualized in vector representation. 6.2b). Let the vector representation guide us now to write another PO operation (see Figure II. looking at Figure II. the vector of momentum of X moves from A remains unaffected.2a we see that. Of course. while the angular z to + y (90o rotation). the unit matrix (label "1") always stays the same.
We now proceed to apply our vector rule for an arbitrary angle (see Figure II. Many pulse sequences contain rotations other than 90o or 180o. This time we ignore the factors p/2N or q/2N. whatsoever) (5) ( p / 2 N )[ x1] (q / 2 N )[1x] 90yA applied to D(1) above: 90 yA ( p / 2 N )[ x1) (q / 2 N )[1x] ( p / 2 N )[ z1] (q / 2 N )[1x] The validity of this approach is demonstrated in Appendix E.The PO Formalism 71 (3) 90yAX (nonselective) pulse applied to D(0): 90 yAX ( p / 2 N )[ z1] (q / 2 N )[1z ] D(0) ( p / 2 N )[ x1] (q / 2 N )[1x] D(1) (4) 90xA applied to D(1) above: 90 xA ( p / 2 N )[ x1] (q / 2 N )[1x] (No change. [ zz ] [ zz ] [ zz ] [ xy ] [1y ] [ zz ] 90 yA 90 yX 90 xA 180 yA 90 xA [ xz ] [ zx] [ yz ] [ xy ] [1 y ] [ zz ]cos [ xz ]sin yA .2c). The PO representation of this rotation is ( p / 2 N )[ z1] (q / 2 N )[1z ] xX ( p / 2 N )[ z1] (q / 2 N )([1z ]cos [1y ]sin ) A few more examples of rotations are given below.
72 Product Operator Treatment z z a (p/2N)[z1] (q/2N)[1z] y 90xX (p/2N)[z1] +(q/2N)[1y] y A x x X A X z z b (p/2N)[z1] (q/2N)[1z] y +(p/2N)[y1] (q/2N)[1z] 90xA y A x x A X z z X c (p/2N)[z1] (q/2N)[1z] y xX (p/2N)[z1] (q/2N)[1z]cos +(q/2N)[1y]sin y A x x A X X Figure II.2. . PO and vector representation of rotations.
by considering separately each factor in the product.. y. For instance.The PO formalism 73 It must be mentioned at this time that only POs containing x. or z for one spin and 1 for the other(s) represent magnetization components along the corresponding Cartesian axes and have a vector representation. Nevertheless. a nonselective pulse xAX applied to the product operator [zy] is treated in the following sequence: [ zy ] xX xA [ zy ]cos 2 [ yy ]sin [ zz ]cos sin [ yy ]sin cos [ yz ]sin 2 [ zy ]cos These two operations may be performed in any order. nonselective pulses affecting n nuclei must be handled in n successive operations. it has 256 elements). .e. In an AMX system (three spin 1/2 nuclei): [ zzz ] 90 yA [ xzz ] AMX [ xzz ] [ xzz ] 180 xM [ xzz ] [ xzz ] 180 xA Nonselective pulses affect more than one nucleus in the system. the rotation applied to all other POs can be treated in the same way as above. i. The great advantage over the density matrix formalism is that we can apply this approach to systems larger than two spins without the considerable increase in the computation volume (for CH3 the matrix is 16x16. For example: [ zz ] [ xz ] [ zzz ] 90 xAX [ yy ] [ xy ] [ xxz ] 90 xAX 90 yAM For rotations other than 90o or 180o.
Step 2: we calculate the effect of coupling. Step 1 (shift evolution) A shift evolution is equivalent to a rotation about the z axis by an angle = t. TREATMENT OF EVOLUTIONS IN THE PRODUCT OPERATOR FORMALISM As shown in Appendix F. II.3. The angle = At.3. Step 1: we consider the system noncoupled (chemical shift evolution only). . Example: [ x1] shift A [ x1]cos A t [ y1]sin A t The analogy with the vector representation is shown in Fig.74 Product Operator Treatment 7. Another example: [ zy ] shift X [ zy ]cos X t [ zx]sin X t The rule of thumb for shift evolution is : PO after evolution = (PO before evolution) cos t + (PO before x for the spin evolution in which x is replaced by y and y by affected by evolution) sin t. PO and vector representation of a coupled evolution. the evolution of coupled spins is conveniently treated in two steps. The labels 1 and z are invariant. y y shift A evolution x D=[x1] x D=[x1] cos + [y1] sin Figure II.
[xyz] .22) becomes [ xyz ] shift A. Examples : [xzz] AMX couplings JAM and JAX are active. but JAM is not. Example: [ xyz ] AMX shift M shift A [ xyz ]cos A A A t [ yyz ]sin M M A t A A [ xyz ]cos [ yyz ]sin t cos t [ xxz ]cos t sin M M t t cos t [ yxz ]sin t sin t (II.22) The X spin is represented by z in the POs. but JMX is not. Therefore the "shift X" does not bring any further change in (II. M. couplings JAX and JMX are active. these evolutions have to be treated as separate steps (the order is immaterial).23) the relation (II. With the notations cos At c sin A cos sin M M t t c' s' cos sin X X t t c" s" t s (II.22).The PO formalism 75 If more than one nucleus in the system is subject to shift evolution. X cc '[ xyz ] cs '[ xxz ] sc '[ yyz ] ss '[ yxz ] One more example : [ xyy ] shift M shift X shift A c[ xyy ] s[ yyy ] cc '[ xyy ] cs '[ xxy ] sc '[ yyy ] ss '[ yxy ] cc ' c "[ xyy ] cc ' s "[ xyx] cs ' c "[ xxy ] cs ' s "[ xxx] sc ' c "[ yyy ] sc ' s "[ yyx] ss ' c "[ yxy ] ss ' s "[ yxx] Step 2 (J coupling evolution) According to the rules presented in Appendix F the coupling between two spins is active only when one of the nuclei appears in the PO with an x or y while the other nucleus is represented by z or 1.
None of them depends on J.1 we see that the evolution frequency for the double4) is (A+J/2)+(XJ/2) = X+A. The zeroquantum quantum transition (1 transition frequency (2 3) is XA. Referring to Figure I.24) System AMX J AM J AX c[ x11] s[ y11] cC[ x11] cS[ yz1] sC[ y11] sS[ xz1] (II. in the case of the two spin system. Product operators as [xx].and z by 1) sin Jt. 1 .25) cCC '[ x11] cCS '[ y1z ] cSC '[ yz1] cSS '[ xzz ] sCC '[ y11] sCS '[ x1z ] sSC '[ xz1] sSS '[ yzz ] Notations for the last two examples: c cos At C cos J AM t C ' cos J AX t (II. Examples: C cos J AX t with [ xz ] J AX C[ xz ] S[ y1] S sin J AX t [ xyz ] J MX J AX C[ xyz ] S[ yy1] S' sin J AM t S sin J AX t Combinations of steps 1 and 2 are illustrated by two examples. a coupled evolution does not split any PO into more than 4 terms. the step 2 rule is: PO after evolution = (PO before evolution) cos Jt + (PO before evolution with x replaced by y. 1 by z. System AM [x1] shift A c[ x1] s[ y1] J AM where CC '[ xyz ] CS '[ xx1] SC '[ yy1] SS '[ yxz ] C ' cos J AM t C cos J AX t cC[ x1] cS [ yz ] sC[ y1] sS[ xz ] [ x11] shift A (II. y by x. This seemingly surprising situation prompts an explanation.26) s sin At S sin J AM t S ' sin J AX t We notice that.and multiplequantum coherences). [xy]. This is due to the fact that when both shifts are active the coupling is not. [xyy] have nonvanishing elements on the secondary diagonal only (which represents zero.76 Product Operator Treatment Another example: [xyy] no coupling is active 1 For every coupling that is active.
b) The coupling between two nuclei is active if both or none of them are affected by the 180o pulse. The routine. can be placed either before or after the pulse (of course. . the pulse applied in the middle of the evolution time te. as shown below." The chemical shift evolution can also be refocused if the pulse is applied on the nucleus that evolves. .The PO formalism 77 8. part of which may be magnetically equivalent. in our calculations. 180 180 During the hypothetical delay. REFOCUSING ROUTINES We have seen in the 2DHETCOR section that the 180xC pulse caused the decoupling of carbon from proton. the following rules apply: a) Only shifts of the nuclei not affected by the 180o pulse are taken into account in the evolution since all other are refocused. . We call this a "refocusing routine. The rules above are demonstrated in Appendix H. this cannot be done in the actual sequence). The above rules are valid for systems of m spin 1/2 nuclei. caused the second half to compensate for the coupling effect of the first half. we move the pulse from the middle of the interval to one of its ends. In other words. The phase of the pulse does not affect the validity of the rules but it must be conserved when. can be handled in the conventional way (evolutionpulseevolution) but the partial results are fairly more complicated than the final result. The 180o rotation is supposed to occur about an axis in the xy plane (no offresonance pulse). 180 We suggest here an efficient calculation shortcut in which the entire evolution time.
For example. changing the sign of y and z and leaving x unchanged. D( n 1) 180 xA p ' cC[ x1] p ' cS[ yz ] p ' sC[ y1] p ' sS[ xz ] q ' c ' C[1x] q ' c ' S[ zy ] q ' s ' C[1y ] q ' s ' S[ zx] D(n 2) The second evolution /2 is calculated as follows D( n 2) shift A p ' c 2 C[ x1] 2 p ' csC[ y1] p ' c 2 S [ yz ] 2 p ' csS[ xz ] p ' scC[ y1] p ' s C[ x1] p ' scS[ xz ] p ' s S[ yz ] q ' c ' C[1x] q ' c ' S[ zy ] q ' s ' C[1y ] q ' s ' S[ zx] shift X p ' c 2 C[ x1] p ' csC[ y1] p ' c 2 S [ yz ] p ' s C[ x1] 2 p ' csS[ xz ] p ' s 2 S[ yz ] p ' scC[ y1] p ' scS[ xz ] q ' c '2 C[1x] q ' c ' s ' C[1y ] q ' c '2 S [ zy ] q ' c ' s ' S [ zx] q ' s ' c ' C[1 y ] q ' s '2 C[1x] q ' s ' c ' S[ zx] q ' s '2 S [ zy ] D(int ) This is an intermediate result. since we still have to consider the effect of Jcoupling.. D ( n) shift X J shift A p ' c[ x1] p ' s[ y1] q '[1x] p ' c[ x1] p ' s[ y1] q ' c '[1x] q ' s '[1 y ] p ' cC[ x1] p ' cS [ yz ] p ' sC[ y1] p ' sS [ xz ] q ' c ' C[1x] q ' c ' S[ zy ] q ' s ' C[1 y ] q ' s ' S [ zx] D(n 1) where c cos s sin A A /2 /2 c ' cos s ' sin X X /2 /2 C cos J / 2 S sin J / 2 The 180xA pulse affects only the first label in the POs (nucleus A). i. /2. we combine the terms containing the . we assume that the density matrix at time t(n) is D ( n) and it is followed by / 2 180 xA /2 pulse evolution.e. p '[ x1] q '[1x] In the conventional way. Before doing so. evolution we start with the first evolution.78 Product Operator Treatment We now compare the conventional calculation with the shortcut.
The PO formalism 79 same PO. only shift X is operative. only the coupling is operative. The X magnetization has evolved with the frequency X during the delay but in the end it is not affected by the Jcoupling.. if the pulse affects all nuclei. D(int ) J p ' C 2 [ x1] p ' CS[ yz ] p ' SC[ yz ] p ' S 2 [ x1] q 'cos X (C 2 [1x] CS [ zy ] SC[ zy ] S 2 [1x]) q 'sin X (C 2 [1y ] CS[ zx] SC[ zx] S 2 [1y ]) p '[ x1] q 'cos X [1x] q 'sin X [1 y ] We now show that this result can be obtained in just two lines by using the shortcut.. fast and slow. JMX. JAX ) are active. D(int ) p '(c 2 s 2 )C[ x1] p '(c 2 s 2 ) S[ yz ] q '(c '2 s '2 )C[1x] 2q ' c ' s ' C[1y ] q '(c '2 s '2 ) S[ zy ] 2q ' c ' s ' S[ zx] We recognize the expressions for the sine and cosine of twice the angle X /2 . If the pulse affects only nucleus A. nucleus A). AMX). X .. Shift A and coupling JAX are refocused (see example above). we calculate the effect of J. Both shifts are refocused. If the pulse affects all nuclei except one (e. we see the effect of shift A and of the couplings which do not involve A. . representing the A magnetization. Following the rules described above.e. If the 180o pulse affects both A and X. i. D(int ) p ' C[ x1] p ' S[ yz ] q 'cos X (C[1x] S[ zy ]) q 'sin X (C[1y ] S [ zx]) Further. while the shift A and the coupling J are ignored). D( n) 180 xA p '[ x1] q '[1x] shift X p '[ x1] q 'cos X [1x] q 'sin X [1 y ] The first term. In a system of two nuclei (A and X) if the pulse affects nucleus A. This is because its two components. we first apply the 180xA pulse.. i. only the couplings are active. all shifts except A and the couplings involving A (JAM . appears unchanged because its evolution during the first delay /2 has been undone during the second /2. then an evolution (where only the shift X is considered.e.g.g. have undergone a change of label in the middle of the delay . In a system of more than two nuclei (e.
5) is: D (0) where p '[ z1] q '[1z ] p' = p/2N q' = q/2N N = number of states = 4 p and q have the same meaning as in (I. The coupling AX is refocused by the 180xA pulse. D(1) te (shift X ) 180 xA p '[ z1] q '[1 y ] (II. PO TREATMENT OF 2DHETCOR: TWO SPINS (CH) We consider again the sequence in Figure I. D(0) 90 xX p '[ z1] q '[1 y ] D(1) (II.80 Product Operator Treatment 9. The density matrix at equilibrium (see II.28) p '[ z1] q 'cos WX te [1 y ] q 'sin WX te [1x] D(4) A coupled evolution 1 follows. which can be handled according to the rules of Section II.2 applied to a system of two weakly coupled spin 1/2 nuclei A and X.8 this routine has the same effect as the 180xA pulse followed by an evolution te during which only the shift X is active.4).27) We apply the "refocusing routine" treatment to the segment te / 2 180 xA te / 2 As shown in Section II.3) and (I.7 with c ' cos X 1 C cos J 1 s ' sin shift X X 1 shift A S sin J same 1 D(4) p '[ z1] q 'cos X e t (c '[1y ] s '[1x]) q 'sin X e t (c '[1x] s '[1 y ]) J p '[ z1] q 'cos X te (c ' C[1 y ] c ' S[ zx] s ' C[1x] s ' S[ zy ]) q ' sin X te (c ' C[1x] c ' S[ zy ] s ' C[1y ] s ' S[ zx]) D(5) .
All product operators other than the four mentioned above are nonobservable terms (NOT).31) X p '[ z1] q '[ zx]cos Since no other r.e. We are also interested in [yz] and [xz] which can evolve into [x1]. multiplied by q' rather than p'). therefore we are interested in the product operators [x1] and [y1] which give MxA and MyA. If the decoupled detection started at t(7). C = 0 and S = 1 p '[ z1] q 'cos X te ( c '[ zx] s '[ zy ]) q ' sin X te ( s '[ zx] c '[ zy ]) (II. the [yz] term would evolve into a combination of [yz] and [xz]. pulse follows we can concentrate on those terms which represent observable magnetization components. The coupled evolution 2 is necessary to render the second term observable.32) 1) The second term is important for the 2D experiment because it is proton modulated (it contains the frequency X). [y1] during a coupled evolution..29) Using the trigonometric relations for the sum of two angles [see (A29) and (A30)] we can rewrite D(5): D(5) p '[ z1] q '[ zx](cos X te cos X 1 sin q '[ zy ](cos X te sin X 1 sin p '[ z1] q '[ zx]cos X (te q '[ zy ]sin 1) X e t sin X 1 ) X te cos X 1) (II. none of which is .f.30) X (te 1) We calculate now the effects of the pulses three and four (in the PO formalism it is simpler to handle them separately): D(5) 90 xA 90 xX (te q '[ zz ]sin X (te 1) 1) D(6) p '[ y1] q '[ yx]cos X (te q '[ yz ]sin X (te 1) 1) D(7) (II.2DHETCOR 81 Since 1 = 1/2J and D(5) J 1= /2. It is also enhanced by polarization transfer (i. We can rewrite D(7) as: D(7) p '[ y1] q '[ yz ]sin X (te NOT (II. We observe nucleus A.
35) In order to maximize the proton modulated term.33) same q 'sin X (te where p '(cC[ y1] cS [ xz ] sC[ x1] sS[ yz ]) 1 )(cC[yz ]cS [x1]sC[xz ]sS [y1])+NOT D(8) c cos s sin A A 2 2 C S cos J sin J 2 2 (II. D(7) shift X shift A p '(c[ y1] s[ x1]) q 'sin J X (te 1 )(c[yz ]s[xz ]) (II.e. It will be shown in Section II. the product operators [x1]. The observable terms [x1] and [y1] can derive from [yz] only in a coupled evolution. At t(8) we have (see Appendix J): MxA(8) = (MoA/p')(coefficient of [x1]) X(te+ 1)cos X(te+ 1)sin A 2 A 2 X(te+ 1) = (q'/p')MoAsin MyA(8) = (q'/p')MoAsin MTA(8) = MxA(8)+iMyA(8) = (q'/p')MoAsin exp(i A 2) (II. We can therefore retain only [x1]. [y1] will evolve into combinations of [x1]. i. one selects for the value 1/2J which leads to S = 1 and C = 0.82 Product Operator Treatment observable. For 2 = l/2J: 2 D(8) q 'sin X (te 1 )( cos A 2 [x1] sin A 2 [y1])+NOT (II... [y1] while the product operators [xz]. the methylene and methyl cases) a shorter 2 is to be used. they will remain nonobservable.34) During the decoupled evolution that follows after t(8). [y1] in the explicit expression of D(8): D(8) p '(cC[ y1] sC[ x1]) q 'sin + NOT X (t e 1 )(cS [x1]sS[y1]) (II.10 that for AX2 and AX3 (e.g.36) The simplest way to describe the decoupled evolution td (from the point of view of the observable A) is a rotation of the transverse magnetization MTA about the z axis.[yz]. This value of 2 represents an optimum in the particular case of the AX system. [yz] evolve into combinations of [xz].37) .
g.38) This is in agreement with the result obtained in Part I through DM calculations. The real advantage will be seen when we apply (see Section II.39) D(0) p '[ z111] q '([1z11] [11z1] [111z ]) for AX 3 Instead of following the two cases separately. we use the "multiplet formalism" introduced in Appendix L. 10.9 to an AX2 or AX3 system (e. D(0) 90 xX ( p '/ n){z1} q '{1z} (II. By handling the decoupled evolution as a magnetization rotation we get M TA (9) M TA (8)exp(i Atd ) (q '/ p ') M oA sin X (te 1 ) exp[i A (td 2 )] (II.10) the PO formalism to an AX2 and AX3 case (e. The calculations requested by the PO approach are somewhat less complicated than those of the DM approach.41) As we did in section II.9.40) ( p '/ n){z1} q '{1y} D(1) (II. The density matrix at equilibrium is: for AX 2 D(0) p '[ z11] q '([1z1] [11z ]) (II. The reader should get acquainted with this formalism before proceeding further. we treat the segment te / 2 180 xA te / 2 . PO TREATMENT OF 2DHETCOR: CH2 AND CH3 We extend the calculations carried out in section II. a methylene or a methyl).. the 2DHETCOR of a CH2 or CH3). D(0) valid for any AXn system.g.2DHETCOR 83 The ratio q '/ p ' X / A represents the enhancement factor through polarization transfer..
e. c ' cos X 1 .45) (II. i.. while formally replacing [ ] by { } and using p'/n instead of p'.84 Product Operator Treatment as a "refocusing routine" and this brings us directly from D(1) to D(4). D(1) 180 xA ( p '/ n){z1} q '{1 y} (II.e. s ' sin X 1 Using again the trigonometric relations for the sum of two angles as we did in (II. {y1} only and take advantage of the exception . s' have the same meaning as in (II.9. rule #4.43) D(5) where c'.30) we rewrite D(5) as: D(5) ( p '/ n){z1} q '{zx}cos D(5) D(6) 90 xX X (te X 1 ) q '{zy}sin 1 X (te X 1 ) (II. For the coupled evolution 2 we can concentrate on the observable terms {x1}.44) 1 ( p '/ n){z1} q '{zx}cos ( p '/ n){ y1} q '{ yx}cos (te (te ) q '{zz} sin ) q '{ yz} sin (te (te ) ) D(6) 90 xA X 1 X 1 D(7) ( p '/ n){ y1} q '{ yz}sin D(7) X (te NOT 1) (II. J X e 1 = /2) we have X e ( p '/ n){z1} q 'cos t {zx} q 'sin t {zy} 1 ( shift X ) ( p '/ n){z1} q 'cos q ' sin X e t (c '{zx} s '{zy}) X e t (c '{zy} s '{zx}) (II..42) te (shiftX) ( p '/ n){z1} q 'cos X te {1y} q 'sin X te {1x} D(4) With the assumption that D(4) 1(J ) 1 1/ 2J (i.46) Up to this point we have followed step by step the calculations in Section II. This procedure is always valid for rotations (pulses) and in this case it was allowed for evolutions as stated in Appendix L.29).
47) n= number of magnetically equivalent X nuclei (e. number of protons in CHn). The value 2 = 1/2J. which implies S = 1 and C = 0.. c cos A 2 C cos J 2 s sin A 2 S sin J 2 In order to separate the effect of shift (c and s) and coupling (C and S) we rewrite D(8) as D(8) ( p '/ n)C n (c{ y1} s{x1}) q 'sin X (te 1 ) SC n 1 (c{x1} s{ y1}) (II. is not suitable anymore because it nulls the useful 2D signal for any n >1. We will discuss later the optimum value of 2.g.48) Here again the second term is the true 2D signal while the first one generates axial peaks in the 2D picture since it does not contain the frequency X.2DHETCOR 85 stated in Appendix L.49) . rule #5. 2 D(7) ( p '/ n)( sC n {x1} cC n { y1}) q 'sin X (te 1 )( cSC n 1 { x1} sSC n 1{ y1}) NOT D(8) (II. MxA(8) = n (nMoA/p')(coefficient of {x1}) A 2 M oAC sin MyA(8) = n nM oA (q '/ p ') SC n 1 sin X (te 1 ) cos A 2 (nMoA/p')(coefficient of {y1}) A 2 M oAC cos nM oA ( q '/ p ') SC n 1 sin X (te 1 )sin A 2 MTA(8) = MxA(8) + iMyA(8) iM oAC n exp(i A 2 ) nM oA (q '/ p ') SC n 1 sin X X (te A 2 1 ) exp(i A 2 ) M oA [iC n n(q '/ p ') SC n 1 sin (t e 1 )]exp(i ) (II. In writing the magnetization components we have to follow the procedure stated as rule #6 in Appendix L.
The optimum 2 values are: n 1 (CH ) 0. Dependence of the factor nSCn1 (S for CH.3/J expressions S.50) The enhancement factor of the 2D term is n(q '/ p ') SC n 1 . In Figure II.196 / J 2 A good compromise is for which all three 2 = 0. and 3SC2 have values exceeding 0.4.9.5 / J 2 n 2 (CH 2 ) 2 0. represented by the term iCn in (II.25 / J (II. The bad news is that this 2 value does not cancel the axial peak. 2SC for CH2.8. M TA (9) M oA [iC M TA (8)exp(i n n(q '/ p ') SC A d n 1 t ) sin X (te 1 )]exp[i A (td 2 )] (II. Figure II.86 Product Operator Treatment The decoupled evolution td during which the detection takes place is treated the same way it was done in II.4 the value of the product nSCn1 is plotted versus 2J for n = 1. Now we can discuss the optimum value of 2.51) n 3 (CH 3 ) 0. as a rotation about Oz. .50). 2 and 3. 2SC. and 3SC2 for CH3 ) on 2 J.
an increased sensitivity of 13C spectra. (II.52) One of the advantages of INEPT is that it allows fast scanning.53) is a recovery factor for carbon (0 . In order to emphasize this feature we will assume that only the protons have fully relaxed in the interval between sequences and will write the initial density matrix as D(0) where ( p '/ n){z1} q '{1z} 1).2 or 3. 90xH 1H 180xC 13 90xC 180xH 90yH Decouple C td t(0) t(1) t(2) t(3) t(4) t(5) t(6) t(7) Figure II. PO TREATMENT OF A POLARIZATION TRANSFER SEQUENCE: INEPT (INSENSITIVE NUCLEI ENHANCEMENT BY POLARIZATION TRANSFER) WITH DECOUPLING We discuss first the decoupled INEPT sequence shown in Figure II. is achieved in two ways: by increasing the peak intensities for the protonated carbons.5. The density matrix at thermal equilibrium is: D ( p '/ n){z1} q '{1z} (II. (limited by the proton relaxation only).5 The INEPT sequence: 90 xH AT 90 yH 90 xC 180 xCH We treat the CHn case with n = 1. Its goal. and by allowing a larger number of scans in a given experiment time.INEPT 87 11.
The optimum value for is 1/4J which leads to sin 2 J = 1.8).56) After t(5) no pulse follows and we can concentrate on the observable terms.59) . D(1) 180 xCH ( p '/ n){z1} q '{1y} 2 ( J coupl . D(5) ( p '/ n){ y1} q '{ yz}sin 2 J NOT (II.54) See Appendix L for the meaning of { } (multiplet formalism). hence.) (II. the necessity of . We will apply a nonselective 180xCH pulse followed by a 2 evolution in which the coupling only is expressed and this will bring us to t(4).57) The second term is enhanced by polarization transfer and it does not depend on . We treat now the portion from t(1) to t(4) as a shiftrefocusing routine (see Section II.58) In D(5) the second term is still not an observable. With this assumption: D(5) ( p '/ n){ y1} q '{ yz} NOT (II.55) q '{zx}sin 2 J ( p '/ n){z1} q '{1 y}cos 2 J D(4) The next two pulses have to be treated successively because one of the terms in D(4) is affected by both the proton and the carbon pulse. keeping in mind that our observe nucleus is 13C. This means the pulse repetition rate is limited only by the proton relaxation as far as the second term is concerned. Using rule #5 in Appendix L we obtain: D(5) ( p '/ n)C n (c{ y1} s{x1}) q ' SC n 1 ( c{x1} s{ y1}) D(6) NOT (II.88 Product Opertator Treatment The effect of the first pulse is D(0) 90 xH ( p '/ n){z1} q '{1 y} D(1) (II. D(4) 90 yH ( p '/ n){z1} q '{1 y}cos 2 J q '{zz}sin 2 J 90 xC ( p '/ n){ y1} q '{1y}cos 2 J D(5) q '{ yz}sin 2 J (II.
60) (II. COUPLED INEPT The coupled INEPT (Figure II.6 The coupled INEPT sequence: 90 xH 90 yH 90 xC AT 180 xCH . This is not alarming since INEPT is not intended as a 2D sequence. with the difference that the proton frequency H is not to be seen.59) has much in common with (II.51).48).61) ]exp[i We focus on the second term in the brackets (polarization transfer and fast scanning).8 H / C . The optimum value of is selected according to Figure II.4 and relations (II. 12. 90xH 1H 180xC 13 90xC 180xH 90yH C td t(0) t(1) t(2) t(3) t(4) t(5) t(6) Figure II.8 .6) is used for spectra editing.48) to (II. Going through the same steps as from (II. leading to nSC n 1 0. The enhancement factor is therefore 0.INEPT 89 Where c cos s sin C C C S cos J sin J The expression (II.50) we get: M TC (6) M TC (7) M oC [ i C n M oC [ i C n n(q '/ p ') SC n 1 ]exp(i n(q '/ p ') SC n 1 C C ) (t d )] (II.
62) the variable td is also contained in C and S and the Fourier transform exhibits a multiplet. while keeping in mind that C and S have the meanings in (II.61) is only formal. A) Polarization enhanced multiplet (term MA) We discuss separately the CH. The signal was a singlet. In (II.63) The resemblance with (II. 2.63).62) for n = 1.90 Product Opertator Treatment The magnetization at t(6) can be written by taking its expression from the previous sequence (II. and CH3 cases. In (II.7a .62) (II. CH2. We split MTC(6) into two terms M TC (6) M oC (q '/ p ') nSC n 1 exp(i MA MB C d t ) iM oC C n exp(i C d t ) (II.61) we had: C S and the detection time td appeared only in the exponential factor outside the brackets. n = 1 (CH case) MA Using (A28) we have S and this leads to MA 1 M oC (q '/ p ')( )[ ei ( 2i C M oC ( q '/ p ') S exp(i C d t ) exp(i Jtd ) exp( i Jtd ) 2i J ) td ei ( C J ) td ] (II.64) and discuss these two terms separately.60) and replacing by td : M TC (6) with M oC [ i C n C cos Jtd cos J n(q '/ p ') SC n 1 ]exp(i S sin Jtd sin J C d t ) (II. we have to discuss the expression (II.65) This is the updown doublet of Figure II. . and 3. In order to see how this multiplet looks like.
two up and two down. We will show that it represents a conventional multiplet. n = 1 (CH case) MB iM oC C exp(i C d t ) . n = 3 (CH3 case) MA We use (A38) and obtain M oC (q '/ p ')3SC 2 exp(i C d t ) MA 3 M oC (q '/ p ')( )[ ei ( 8i ei ( C C 3 J ) td ei ( e i( C C J ) td (II.7c: four lines of equal intensities. B) Residual nonenhanced multiplet (term MB) The term MB in (II.67) 3 J ) td J ) td ] This is the peculiar quartet in Figure II.INEPT 91 For a methylene n = 2 (CH2 case) MA Using (A36) we have SC and MA 1 M oC (q '/ p ')( )[ ei ( 2i C M oC ( q '/ p ')2SC exp(i C d t ) exp(2i Jtd ) exp( 2i Jtd ) 4i 2 J ) td ei ( C 2 J ) td ] (II.7b).64) is smaller than MA (no polarization enhancement and < 1).66) This is a triplet with the central line missing and the other two lines one up and one down (see Figure II.
.70) a regular looking quartet (see Figure II. It is shown in Section II.65) through (II. as shown in Figure II. When the term MB is not vanishingly small.70) contain the factor 1/i (or i) .7f).92 Product Opertator Treatment Using (A27) and i = 1/i we obtain 1 M B M oC ( )[ei ( C 2i J ) td ei ( C J ) td ] (II.68) the regular doublet in Figure II.13 that we have a similar situation with the DEPT sequence and a two step phase cycling is sufficient to cancel the residual nonenhanced signal. it breaks the symmetry of the multiplet. n = 3 (CH3 case) MB We use (A37) and obtain 1 M B M oC ( )[ei ( C 3 J ) td 8i J ) td 2e i C td ei ( C 2 J ) td ] (II.7d . n = 2 (CH2 case) MB iM oC C 2 exp(i C d t ) Using (A35) we obtain the triplet 1 M B M oC ( )[ei ( C 2 4i as in Figure II. This drawback can be eliminated by means of an appropriate phase cycling. We notice that all the expressions (II.7e .69) iM oC C 3 exp(i C d t ) 3ei ( C J ) td 3ei ( C J ) td ei ( C 3 J ) td ] (II.7 (g through i). indicating that the respective magnetizations are along the y axis.
7.b.c C Polarization enhanced multiplet (term M A ).e. d.i Actual spectrum (term M A MB) .f Residual nonenhanced multiplet (term M B ). a.INEPT 93 J 2 a d g CH b J e h CH 2 J c J J 2 f i CH 3 C Figure II. C Coupled INEPT.h. g.
The recycle time has to be longer than the proton relaxation time but can be fairly shorter than the carbon T1.53)] D(0) 90 xH ( p '/ n){z1} q '{1 y} D(1) (II. 180xH 90xC 1/2J 180xC yH 1/2J AT(dec The initial density matrix is D(0) where ( p '/ n){z1} q '{1z} (II.71) is a recovery factor for carbon [see (II. CH2. 90xH 1H 90xC 13 180xC 1/2J 1/2J 180xH ± yH Decouple C 1/2J td t(0) t(1) t(2) t(3) t(4) t(5) t(6) t(7) Figure II. The basic (onedimensional) DEPT sequence: 90xH 1/2J ). PO TREATMENT OF DEPT (DISTORTIONLESS ENHANCEMENT POLARIZATION TRANSFER) DEPT is a onedimensional sequence used as a tool for unambiguous identification of the CH.8.94 Product Operator Treatment 13.72) .8. The sequence is shown in Figure II. and CH3 peaks in a proton decoupled 13C spectrum. The nonprotonated carbons will not show up in a DEPT spectrum. It shares with INEPT the advantage of permitting a fast repetition rate.
DEPT 95 For the evolution we use the notations c cos s sin C C / 2J / 2J c ' cos s ' sin H H / 2J / 2J C S cos J / 2 J cos / 2 0 /2 1 (II.3. using the corresponding subscripts 1. Do (3) D1 (3) D2 (3) D3 (3) p '[ y ] p '[ y1] q ' c '[ yx] q ' s '[ yy ] p '[ y11] q ' c '([ yx1] [ y1x]) q ' s '([ yy1] [ y1 y ]) p '[ y111] q ' c '([ yx11] [ y1x1] [ y11x]) q ' s '([ yy11] [ y1 y1] [ y11y ]) (II. ( p '/ n){z1} q '{zx} (II. For completeness. Here.76) .73) sin J / 2 J sin In treating the evolution.75) ( p '/ n){ y1} q ' c '{ yx} q ' s '{ yy} D(3) The multiplet formalism { } can help us only so far.74) ( p '/ n){z1} q ' c '{zx} q ' s '{zy} D(2) D(2) 90 xC 180 xH ( p '/ n){z1} q ' c '{zx} q ' s '{zy} (II. we will also consider the case of the nonprotonated carbon (subscript zero).2. and CH3. Rule #5 in Appendix L). D(1) shift H J coupl. the shift and coupling may be handled in any order. because of the particular values of C and S. we are better off by starting with the coupling. It does not apply to the coupled evolution of terms like {zx} or {yx} since this coupled evolution is followed by some more pulses (cf. We have to consider separately the CH. CH2.
D2 (3) cpl AX1 p '[ xz1] q ' c '([ yx1] [ xzx]) q ' s '([ yy1] [ xzy ]) p '[ yzz ] q ' c '( [ xxz ] [ xzx]) q ' s '([ xyz ] [ xzy ]) p '[ yzz ] q ' c '2 ( [ xxz ] [ xzx]) q ' c ' s '( [ xyz ] [ xzy ]) q ' s ' c '( [ xyz ] [ xzy ]) q ' s '2 ([ xxz ] [ xzx]) cpl AX 2 shift H p '[ yzz ] q '([ xxz ] [ xzx]) shift C p '(c[ yzz ] s[ xzz ]) q ' c([ xxz ] [ xzx]) q ' s([ yxz ] [ yzx]) D2 ( 4 ) We were allowed to handle the evolution of both protons in one step only because none of the POs had x or y for both protons. i. p '[ xz ] q '(c '[ yx] s '[ yy ]) p '[ xz ] q '(c '2 [ yx] c ' s '[ yy ] s ' c '[ yy ] s '2 [ yx]) p '[ xz ] q '[ yx] shift C p '(c[ xz ] s[ yz ]) q '(c[ yx] s[ xx]) D1 (4) In processing the evolution of D2(3) we have to treat separately the coupling of the carbon with the first and with the second proton. only one proton was affected by the evolution in each PO.77) p '( c[ yzz ] s[ xzz ]) q ' c ([ xxz ] [ xzx ]) q ' s ([ yxz ] [ yzx]) D3 (4) p '(c[ xzzz ] s[ yzzz ]) q ' c([ yxzz ] [ yzxz ] [ yzzx]) q ' s ([ xxzz ] [ xzxz ] [ xzzx]) . Similar calculations will produce D3(4). Summarizing the results at t(4) we have: Do (4) D1 (4) D2 (4) p '(c[ y ] s[ x]) p '( c[ xz ] s[ yz ]) q ' c[ y x] q ' s[ xx] (II.e.96 Product Operator Treatment The evolution from t(3) to t(4) leads to Do (3) D1 (3) shift H shift C p '(c[ y ] s[ x]) Do (4) (no coupling) J coupl..
sin( sin( Do (5) ) ) sin sin p '( c[ y ] s[ x]) (the proton pulse has no effect). We take also into account that cos( cos( Do (4) 180 xC ) cos ) cos . [yx]. separately on the two protons (see end of Section II. which is neither 90o nor 180o.[y1])and the potentially observable terms ([xz]. We have relegated terms as [xx]. D2 (4) 180 xC p '(c[ yzz ] s[ xzz ]) q ' c([ xxz ] [ xzx]) q ' s ([ yxz ] [ yzx]) yX 1 p 'cos (c[ yzz ] s[ xzz ]) q 'cos ( c[ xzx] s[ yzx]) q 'sin (c[ xzz ] s[ yzz ]) NOT p 'cos 2 (c[ yzz ] s[ xzz ]) q 'cos sin (c[ xzz ] s[ yzz ]) q 'sin cos (c[ xzz ] s[ yzz ]) NOT yX 2 p 'cos 2 (c[ yzz ] s[ xzz ]) 2q 'cos sin (c[ xzz ] s[ yzz ]) NOT = D2(5) . we will treat it as a rotation about the yaxis with alternate signs of . [xy].[yz]).DEPT 97 The y pulse is mathematically equivalent to a y pulse. as described in Appendix K. In processing D2(4) we have to calculate the effect of the proton pulse. D1 (4) yH 180 xC p '( c[ xz ] s[ yz ]) q ' c[ y x] q ' s[ xx] p 'cos ( c[ xz ] s[ yz ]) q 'sin (c[ y z ] q ' s[ xz ] NOT = D1(5) In the last calculation we have retained only the observable terms ([x1]. Therefore.6). [yy] to the NOT bunch (nonobservable terms). .
when the acquisition begins. we notice that no chemical shift (proton or carbon) is expressed in the density matrix at time t(6). Do (5) D1 (5) shift C (II.98 Product Operator Treatment Similar calculations have to be performed on D3(4) and the situation at t(5) is Do (5) D1 (5) D2 (5) p '( c[ y ] s[ x]) p 'cos ( c[ xz ] s[ yz ]) q 'sin (c[ y z ] q ' s[ xz ] NOT p 'cos 2 (c[ yzz ] s[ xzz ]) 2q 'cos sin (c[ xzz ] s[ yzz ]) NOT D3 (5) lp 'cos3 q(c[ xzzz ] s[ yzzz ]) 3q 'cos 2 q sin q( c[ yzzz ] s[ xzzz ]) NOT Follows now the last 1/2J coupled evolution. . p 'cos ( c[ y1] s[ x1]) q 'sin ( c[ x1] s[ y1] NOT shift C p 'cos ( c 2 [ y1] cs[ x1] sc[ x1] s 2 [ y1]) q 'sin ( c 2 [ x1] cs[ y1] sc[ y1] s 2 [ x1]) NOT p 'cos [ y1] ( q 'sin [ x1]) NOT=D1 (6) After performing similar calculatons for D2(5) and D3(5). This alone can justify the "distortionless" claim in the name of the sequence.78) p '( c 2 [ y ] cs[ x] sc[ x] s 2 [ y ]) p '[ y ] Do (6) p '[ y ] coupl.79) As a remarkable achievement of the DEPT sequence. We will not have any frequency dependent phase shift. We will retain only the observable terms. we can summarize the results at t(6) as follows Do (6) D1 (6) D2 (6) D3 (6) p '[ y ] ( p 'cos [ y1] q 'sin [ x1]) NOT ( p 'cos 2 [ y11] 2q 'sin cos [ x11]) NOT ( p 'cos3 [ y111] 3q 'sin cos 2 [ x111]) NOT (II. having x or y for carbon and 1 for all protons.
respectively. The discrimination between CH.8) being applied along the +y and y axis. with different values of the flip angle . . sin = 1 and (II.DEPT 99 can be relatively small when a high The term containing repetition rate is used. which does not contain the factor and is also polarization enhanced (has q' rather than p'). When is slightly larger or smaller than 90o. the first term is cancelled and we are from the one with phase left with D1 (6) q 'sin [ x1] NOT D2 (6) 2q 'sin cos [ x11] NOT D3 (6) 3q 'sin cos 2 (II. If we take a scan with the phase +y and subtract it y. a twostep phase cycling is enough. Theoretically. We are interested in the second term. a CH2 will appear as a small singlet.80) becomes D1(6) = q'[x1]) + NOT D2(6) = NOT D3(6) = NOT This is a 13C spectrum in which only the CH lines appear.80) [ x111] NOT The subtraction is performed by a 180o shift in the receiver phase. 45o and 135o. negative or positive. then cos = 0 . respectively. CH2. and CH3 is done by running the sequence three times. That is why DEPT is a good method for calibrating the 90o proton pulse in a spectrometer configured for observing carbon. namely 90o. When = 90o. The nonprotonated carbons do not appear in the phasecycled spectrum. The sin factor in the expression of the density matrix corresponds to the last proton pulse (see Figure II. The first term can be edited out by phase cycling. in which the phase of the last proton pulse is y +y and the receiver phase is 180o 0o Additional phase cycling is commonly used to cancel radiofrequency interferences and the effect of pulse imperfections.
sin = 1/ 2 and (II. CH) while eliminating the peaks of the other two groups (CH2 and CH3). This is theoretically based on linear combinations of the spectra obtained with different values of (45o. When becomes = 135o. and CH3 peaks. 135o). which is oriented along x at t(6). a normal run is needed with a long recycle time.. when the acquisition begins.g. and CH3 peaks for each of the three angles. . The 13C magnetization. will precess during the acquisition with the Larmor frequency corresponding to the respective line and will appear as a singlet. The 45o run is necessary when one wants to do spectral editing. Table II.2 contains the relative amplitudes of CH.80) becomes D1(6) = (1/ 2 )q'[x1]) + NOT D2(6) = q'[x11] + NOT D3(6) = (3/ 2 2) q'[x111]) + NOT All CH. CH2 .80) D1(6) = (1 / 2 )q'[x1]) + NOT D2(6) = q'[x11] + NOT D3(6) = (3/ 2 2) q'[x111]) + NOT This is the same situation as for 45o.100 Product Operator Treatment When = 45o. sin = 1/ 2 and (II. We have discussed all the features of DEPT using the expression of the density matrix at time t(6). and CH3 appear as positive singlets. CH2. CH2 . 90o. For the nonprotonated carbons. then cos = 1/ 2 . Modern instruments offer the possibility to edit DEPT spectra in order to select only the peaks of one group (e. but CH2 peaks appear negative. In principle only the 90o and the 135o runs are sufficient for an unambigous identification of the CH. cos = 1/ 2 .
Relative peak amplitudes in the raw DEPT spectra.3.1.06) 0 1 0 3 2 2 B 90o 1 1 2 (0. Spectrum A CH 1 2 (0.12 Sum of the above Some instrument softwares make it possible to alter the theoretical coefficients in order to compensate for hardware imperfections.707) C 135o (1.3 shows the operations necessary to obtain spectrs of only one of the three groups or all of them together (note that the spectrum taken at 45o also shows the peaks of all groups.DEPT 101 Table II. Table II.41B)/2. .2. Linear combinations of the raw DEPT spectra. Combination B (A C)/2 CH 1 0 0 1 CH2 0 1 0 1 CH3 0 0 1 1 (A+C . but not their true amplitudes).707) CH2 1 CH3 3 2 2 45o (1. necessary in order to obtain only one of the three groups or all of them together.06) Table II.
102 Product Operator Treatment 14. CH2.81) . 1H Decouple 90xC 180yC 1/J Decouple 13 C 1/J td t(0) t(1) t(2) t(3) t(4) t(5) Figure II.9. The sequence can be correctly analyzed within the frame of the vector representation. Do (0) D1 (0) D2 (0) D3 (0) p '[ z ] p '[ z1] q '[1z ] p '[ z11] q '([1z1] [11z ]) p '[ z111] q '([1z11] [11z1] [111z ]) (II. PO TREATMENT OF APT (ATTACHED PROTON TEST) APT is probably the first sequence designed to identify the number of hydrogen atoms attached to each carbon in a decoupled 13C spectrum. with the exception of one specific 1/J delay. The APT sequence: 90xC (decouple) AT(decouple) 1/J 180yC 1/J We will treat separately the C. denoting the respective density matrices with subscripts 0 to 3.9. The broadband proton decoupler is kept permanently on. Here we treat it with the PO formalism. The sequence is shown in Figure II. and CH3 systems. CH. The sequence is relatively simple and does not involve proton pulses.
We start therefore with Do (0) D1 (0) D2 (0) D3 (0) p '[ z ] p '[ z1] NOT p '[ z11] NOT p '[ z111] NOT (II. the proton components do not have a predictable behavior during the delay in which the decoupler is turned on (see Figure II. AX 2 D2 (1) coupl. Do (0) D1 (0) D2 (0) D3 (0) 90 xC 90 xC 90 xC 90 xC p '[ y ] Do (1) p '[ y1] NOT=D1 (1) p '[ y11] NOT=D2 (1) p '[ y111] NOT=D3 (1) (II. AX 2 D3 (1) coupl. We can treat them as NOT (nonobservable terms).APT 103 Since no coherent proton pulse is applied throughout the sequence.84) we summarize the results at t(2).83) For the evolution 1/J we use the notations c cos s sin Do (1) D1 (1) shift C C C /J /J .82) Anyhow. AX 1 shift C p '[ y11] NOT p '(c[ y11] s[ x11]) NOT=D2 (2) p '[ y111] NOT p '[ y111] NOT p '(c[ y111] s[ x111]) NOT=D3 (2) coupl. C S cos J / J cos 0 1 sin J / J sin p '(c[ y ] s[ x]) p '[ y1] NOT Do (2) coupl. It is not necessary . AX 1 coupl. we can anticipate that the proton POs will never turn into 13C observables. shift C p '(c[ y1] s[ x1]) NOT=D1 (2) p '[ y11] NOT coupl. AX 3 shift C p '[ y111] NOT In (II. .9).
Even with the sequences that cannot be handled with the vector representation alone. it may be instructive to follow the evolution of the magnetization components as indicated by the density matrix expressions. the PO treatment is less instructive about how this has been achieved than the vector representation.104 Product Operator Treatment to carry the NOT any farther. It comes from the fact that.84) We observe that the density matrices for CH and CH3 have a minus sign. . Do (2) D1 (2) D2 (2) D3 (2) p '(c[ y ] s[ x]) p '(c[ y1] s[ x1]) p '(c[ y11] s[ x11]) p '(c[ y111] s[ x111]) (II. We have done this in Section 3.84) At t(4) the detection starts. in order to avoid frequency dependent phaseshifts. This is exactly what the APT is meant to do. Admittedly.11 of Part I. All peaks will be singlets (decoupled acquisition) but CH and CH3 will be negative. the coupling to each proton reverses the sign (C = 1). Do (2) D1 (2) D2 (2) D3 (2) shift C 180 yC 180 yC 180 yC 180 yC p '(c[ y ] s[ x]) p '(c[ y1] s[ x1]) Do (3) D1 (3) D2 (3) D3 (3) p '(c[ y11] s[ x11]) p '(c[ y111] s[ x111]) Now we have the 1/J coupled evolution Do (3) p '(c 2 [ y ] cs[ x] sc[ x] s 2 [ y ]) p '[ y ] Do (4) It works the same way for the other three cases and at t(4) we have Do (4) D1 (4) D2 (4) D3 (4) p '[ y ] p '[ y1] p '[ y11] p '[ y111] (II. The following pulse and delay are only intended to refocus the shift evolution. during the evolution 1/J.
Math Reminder 105 APPENDIX A: MATH REMINDER Complex numbers A complex number z x iy (A1) can be graphically represented as in Figure A. z sin (A3) z z cos i z sin z (cos i sin ) (A4) Using Euler's formula [see (A11)(A16)]. z exp(i ) (A5) x iy z exp( i ) is called the complex . Graphic representation of a complex number z = x+iy.1. where Im z y z Re x Im is the imaginary axis Re is the real axis x is the real part of z y is the coefficient of the imaginary part of z z is the modulus (absolute value) of z is the argument of z Figure A. according to (A1). i 1 is the imaginary unit. one obtains: z The complex number z* conjugate of z.1. The number z is fully determined when either x and y or z and are known. The relations between these two pairs of variables are (see lower triangle): x z cos (A2) y Thus.
2.106 Appendix A Elementary rotation operator Consider a complex number r which has a modulus r = 1 and the argument : r exp(i ) cos i sin (A6) Multiplying a complex number such as z z exp(i ) by r leaves the modulus of z unchanged and increases the argument by : zr z ei eia z ei ( ) (A7) Equation (A7) describes the rotation of the vector Oz by an angle (see Figure A. the rotation operators in the density matrix treatment of multipulse NMR are of the same form as our elementary operator [cf.(B45)]. the elementary rotation operator.2). We can call r. rz z 0 Figure A. . Effect of the rotation operator r = exp(i complex number z = zexp(i ). ) on the Note: Although more complicated.
Effect of the rotation operator . The operator +i would rotate z by 90o CCW.3. .90o = 90o zr Figure A. z z (cos 90o i sin 90o ) i z (A8) r The product cos( 90 ) i sin( 90 ) o o i (A9) zr i z ( i) z (A10) is a real number (its argument is zero). Powers of i (the "star of i") Since i represents a 90o CCW rotation.3) 90o . an i2 operator ( 1) orients the vector in opposite direction. Two consecutive multplications by i result in a 180o rotation. Example 2. In other words.Math Reminder 107 Example 1. z = .4). from (A4 and A6). successive powers of i are obtained by successive 90o CCW rotations (see Figure A. A Let 90o (clockwise) rotation (see Figure A. i 90 o Equation (A10) tells us that the particular operator i effects a 90o CW (clockwise) rotation on the vector z. 90o Then.
.. (A14) . The ex series is ex = 1 + x + x2/2! + x3/3! + . . The star of i. . . cos x.. . x6/6! + . . Figure A.. Series expansion of ex. . i .108 Appendix A i. . 2 6 i . sin x.... (A12) (A13) ix3/3! + x4/4! + ix5/5!. and eix The exponential function describes most everything happening in nature (including the evolution of your investment accounts). i . o 4 8 i 5/2 i 7/2 i 3. .. . .4. . i 3/2 i 1/2 5 i .. i 7. (A11) The sine and cosine series are: sin x = x cos x = 1 The eix series is: eix = 1 + ix x2/2! x3/3! + x5/5! x2/2! + x4/4! x7/7! + . i . i .
A . . . ann Square matrix a11 a21 A a11 a12 . The following formats of matrices are used in quantum mechanics: a11 a21 A . .) Recognizing the sine and cosine series one obtains the Euler formula eix Matrix algebra cos x i sin x (A16) Matrices are arrays of elements disposed in rows and columns. multiplication and inversion. an1 a12 a22 . . . an 2 . Matrix addition . they obey specific algebraic rules for addition. (A15) + i(x x3/3! + x5/5! . an1 Row matrix Column matrix Row and column matrices are also called row vectors or column vectors. a1n . . . . . . . Note that the first subscript of each element indicates the row number and the second. . . .Math Reminder 109 Separation of the real and imaginary terms gives eix = 1 x2/2! + x4/4! x6/6! + . . the column number. . . . a1n a2 n .
2. Matrix multiplication In the following are shown three typical matrix multiplications.e.110 Appendix A Two matrices are added element by element as follows: a11 a21 a31 a12 a22 a32 a13 a23 a33 b11 b12 b13 b23 b33 a11 b11 a21 b21 a31 b31 a12 b12 a22 b22 a32 b32 a13 b13 a23 b23 a33 b33 b21 b22 b31 b32 Only matrices with the same number of rows and columns can be added..3) Example: 1 2 3 4 5 6 7 8 9 1 2 3 14 32 50 Each element of the first line of the square matrix has been multiplied with the corresponding element of the column matrix to yield the first element of the product: 1 1 2 2 3 3 14 b) Row matrix times square matrix: . a) Square matrix times column matrix: a11 a21 a31 a12 a22 a32 a13 a23 a33 b11 b21 b31 3 c11 c21 c31 c11 c21 c31 a11b11 a12b21 a13b31 a21b11 a22b21 a23b31 i. c j1 a31b11 a32b21 a33b31 a jk bk1 k 1 ( j 1.
Math Reminder 111 b11 a11 a12 a13 b12 b13 b23 b33 3 b21 b22 b31 b32 c11 c12 c13 c11 c12 c13 a11b11 a12b21 a13b31 a11b12 a12b22 a13b32 i. 2.e.. The number of columns of the left matrix must match the number of rows of the right matrix. row 2 of the left hand matrix and column 3 of the right hand matrix are involved in the obtaining of the element c23 of the product.3) a11 a21 a31 a12 a22 a32 a13 a23 a33 b11 b12 b13 b23 b33 c11 c12 c13 c23 c33 b21 b22 b31 b32 3 c21 c22 c31 c32 c jm k 1 a jk bkm For instance. c1 j a11b13 a12b23 a13b33 c) Square matrix times square matrix: a1k bkj k 1 ( j 1. In general the matrix multiplication is not commutative: . Example: 0 1 0 1 1 0 1 2 0 1 0 i 1 0 2 i 0 0 0 i 0 i 0 1 i 2 0 i/2 0 i/2 i 0 i 0 0 0 0 i 0 i/2 0 i/2 The product inherits the number of rows from the first (left) matrix and the number of columns from the second (right) matrix.
Example: Find the inverse of matrix A. . Any matrix remains unchanged when multiplied with the unit matrix: 1 Matrix inversion A A 1 A (A21) The inverse A 1 of a square matrix A is defined by the relation: A A 1 A 1 A 1 (A22) To find A 1 : 1) Replace each element of A by its signed minor determinant. 2) Interchange the rows and the columns (this operation is called matrix transposition) 3) Divide all elements of the transposed matrix by the determinant of the original matrix A. one has to multiply it by 1 whenever the sum j+k is odd.112 Appendix A AB It is associative: BA ABC (A17) (A18) (A19) A( BC ) ( AB)C and distributive: A( B C ) The unit matrix is shown below AB AC 1 1 0 0 0 0 1 0 0 0 0 1 0 0 0 0 1 (A20) It must be square and it can be any size. To have the signed minor determinant. The minor determinant of the matrix element ajk is built with the elements of the original matrix after striking out row j and column k.
obtaining: 1/ 2 2/2 1/ 2 2) The transposition yields: 2/2 0 2/2 1/ 2 2/2 1/ 2 1/ 2 2/2 1/ 2 3) Calculate the determinant of A: det(A) = 0 + (1/4) + (1/4) 2/2 0 2/2 1/ 2 2/2 1/ 2 0 + (1/4) + (1/4) = 1 .Math Reminder 113 1 2 2 0 2 1 2 1 1/ 2 2/2 1/ 2 2/2 0 2/2 1/ 2 2/2 1/ 2 A 1 2 1 1) We replace a11 by a22 a32 a23 a33 0 2/2 2/2 1/ 2 0 (1/ 2) ( 2 / 2) ( 2 / 2) 1/ 2 This is the minor determinant obtained by striking out row 1 and column 1 of the original matrix. We replace a12 by a21 a31 [( a23 a33 2/2 1/ 2 2/2 1/ 2 2 / 2) (1/ 2) ( 2 / 2) (1/ 2)] 2/2 and so on.
Example .114 Appendix A Divided by 1. b) In our calculations we will need only inversions of rotation operators: (R R 1) Here is the shortcut: 1) Transpose R (vide supra) 2) Replace each element with its complex conjugate. the transposed matrix remains unchanged: 1/ 2 2/2 0 2/2 A 1/ 2 2/2 1/ 2 1 1 1 2 2 1 1 2 0 2 1 2 1 A 1 2/2 1/ 2 Check: A 1 1 2 2 1 0 2 1 2 1 1 2 1 2 1 1 0 0 0 1 0 0 0 1 2 0 2 1 2 1 2 4 0 0 1 0 4 0 4 0 0 4 1 Note: You will be pleased to learn that: a) There is a shortcut for the inversion of rotation operator matrices because they are of a special kind.
Another example: R 1 0 i 0 1 0 1 0 i 2 i 0 1 0 0 i 0 1 (1) Transpose: you obtain the same matrix (2) Conjugate: . the matrix elements remain the same: 1 2 0 2 1 2 1 R 1 1 2 2 1 Note: This is the same matrix as in the previous example.Math Reminder 115 1 2 2 0 2 1 2 1 R 1 2 1 1) Transpose: 1 1 2 2 1 0 2 1 2 1 2 2) Conjugate: Because they are all real. allowed us to use the shortcut procedure. its being a rotation operator matrix.
For all rotation operators. every element below the main diagonal is the complex conjugate of its symmetrical element above the diagonal d nm * d mn (A24) while the diagonal elements are all real. The derivative of a matrix (e.g. In a Hermitian matrix.. by transposition and conjugation. the Hamiltonian and density matrix are all Hermitian (the rotation operators never are). R 1 R adj (A23) In other words. performed by multiplying or dividing every element of the matrix. our short cut for inversion is equivalent with finding the adjoint of R [see (A23)]. When A = Aadj we say that the matrix A is self adjoint or Hermitian. Trigonometric relations Sum of squared sine and cosine . The angular momentum. The matrix algebra operations encountered in Part 1 of this book are mostly multiplications of square matrices (density matrix and product operators). Inversion is only used to find reciprocals of rotation operators.116 Appendix A R 1 1 1 0 2 i 0 0 1 0 i i 0 1 0 0 i 0 1 Note: The matrix resulting from the transposition followed by complex conjugation of a given matrix A is called the adjoint matrix Aadj. Frequently used is the multiplication or division of a matrix by a constant. with respect to time) is obtained by taking the derivative of each matrix element .
Math Reminder 117 sin 2 sin( cos( ) ) cos 2 sin cos 1 (A25) Negative angles (A26) Expressing sine and cosine in terms of exponentials cos ei e 2 e 2i i (A27) i sin ei (A28) i Demo: Use Euler's formula (A16) e Sum and difference of two angles cos i sin sin( cos( ) sin cos ) cos cos Demo: cos sin sin sin (A29) (A30) z1 z2 ei e i cos cos i ) i sin i sin z1 z1 e i( (cos i sin )(cos i sin ) cos sin ) (cos cos sin sin ) i (sin cos cos( ) i sin( ) Angle 2 sin 2 2sin cos (A31) .
118 Appendix A cos 2 cos 2 sin 2 = 2 cos 2 1 (A32) Demo: Make Angle 3 in (A29).(A30).(A30). Note the 121 triplet structure in (A 35). Relations used for AX3 systems cos3 cos 2 cos 3 sin 3cos 4 sin 3 4 3sin e 3i 3ei e 3i 3e i 8 ei e 8i e i 3i (A37) e 3i (A38) Demo: (A37) is a corollary of (A34). Relations used for AX2 systems 1 cos 2 cos 2 sin 2 cos sin 2 2 e 2i e 2i 2 e 4 e 2i 4i 2i (A35) (A36) Demo: (A35) is a corollary of (A32) and (A36) is a corollary of (A31). Relations used for AX systems cos cos cos( ) cos( 2 ) (A39) . Relation (A38) can be obtained by rewriting (A33) as sin 3 3 sin 4 sin (1 cos2 ) 4 sin cos2 sin Note the 1331 quartet structure in (A37). then use (A31). Use (A25) for the last form. (A28) to obtain the exponential form. Use (A27). sin 3 cos 3 3sin 4 cos3 4sin 3 3cos (A33) (A34) Demo: Make =2 in (A29).(A32) and eventually (A25).
Math Reminder 119 sin sin sin sin sin cos cos( cos( sin( ) cos( 2 ) cos( 2 ) sin( 2 ) ) ) (A40) (A41) (A42) Demo: Introduce (A29) or (A30) in the second member of the equalities above. .
Similar equations can be written for every component and for every nucleus in the system.120 Appendix B APPENDIX B: DENSITY MATRIX FORMALISM Wave functions and density matrix The density matrix is a tool used to describe the state of a spin ensemble as well as its evolution in time. may be expressed as a linear combination of the eigenstates n of the system: . The x component of the magnetic moment of nucleus A has the expectation value: I xA (B1) xA xA A where IxA is the operator of the xcomponent of the angular momentum of nucleus A in the given system. For instance.. In the Schrödinger representation IxA is a time independent operator. It allows the passage from the probabilistic treatment of a system of a few spins to the statistical treatment of a large ensemble of such systems. in turn. Let us concentrate on one of the nuclei in the system (e.g. in an AX system the IxA matrix is 0 1 0 0 1 1 0 0 0 2 0 0 0 1 0 0 1 0 [see (C12)] In order to calculate the macroscopic magnetization. This. Since we are interested in the magnetization we want to express this observable in terms of the wave function of the system. nucleus A). therefore the time dependence of MxA is contained in the wave function of each system. equal to the number of A spins per unit volume. we have to take the average (denoted by a bar) over the whole ensemble: M xA No xA No A I xA (B2) where No is the number of systems per unit volume.
In order to introduce these coefficients in the expression (B2). . . Using the expressions for page. . . IxA. I N1 I12 I 22 . I NN The subscript "xA" has been omited to simplify the writing. The "ket" is a column matrix: c1 c2 . . and on the previous . . I11 I 21 . * cn The angular momentum operator IxA is an N by N square matrix. . . IN 2 . so the time dependence is contained only in the coefficients cn. . . cn The "bra" is a row matrix * c1 * c2 . we put I xA in matrix form. .Density Matrix Formalism 121 N cn n n 1 N=number of quantum states of the system Here again we observe that the eigenfunctions n are time independent (solutions of the time independent Schrödinger equation). . I1N I2N . we obtain: . . .
IN 2 . I NN c* N c1 c2 . . . . . Therefore * in (B4) only the product cmcn has to be averaged over the ensemble and we get . . They are identical for all the systems in our macroscopic ensemble. . The matrix elements Imn are characteristic for the system. I N m cm m (B4) We have obtained a compact expression of I xA In order to introduce it in the expression (B2) of the magnetization we have to take its average over the whole ensemble of systems. n m * cn I nm cm n m * I nm cm cn . I1N I2N . .122 Appendix B I xA * c1 * c2 . * cn . I N1 I12 I 22 . . . . . I1m cm m I 2 m cm m * c1 * c2 . . . cN I11 I 21 . . .
Multiply the sum by No A . . arranged in a square table. Density matrix and magnetizations We rewrite (B5) making use of the expression (B7) M xA No A n m I nm d mn N o A n m * I nm d nm (B8) Relation (B8) represents the practical mode of calculating an observable magnetization component (in our case MxA) when the density matrix D is known: Multiply every matrix element of IxA with the complex conjugate of the corresponding element of D and add all the products. d N1 with We notice that d nm d12 d 22 . form the density matrix: d11 d 21 D . D is a Hermitian matrix. . . .Density Matrix Formalism 123 M xA No A n m * I nm cm cn (B5) where Inm are the matrix elements of the operator IxA. dN 2 . . . . . There are N2 such products which. i. . . . The only time variable elements in (B5) are the averaged products * cm cn . * cm cn d1N d2 N . . d NN (B7) (B6) d mn * d mn ..e. It is convenient to express the factor No equilibrium magnetization MoA: A in terms of the .
In accordance with our sign convention (negative ) this can be rewritten as p and (B10) becomes Bo kT A (B12) M oA The factor N o form A No A p 4 in (B8) can now be written in the more convenient No A 4 M oA p 4 M oX q (B13) For nucleus X (see I.4) the factor is No X Let us apply the "recipe" for finding the magnetization components to the system AX (two spin 1/2 nuclei).124 Appendix B M oA No 2 2 A I ( I 1) Bo 3kT (B9) Note that MoA is always a positive quantity. the absolute value of the equilibrium magnetization for nucleus A. The number of states is N=4 and the (Hermitian) density matrix has the rank 4: . For I = 1/2 the expression (B9) becomes: M oA No 2 2 A Bo 4kT (B10) In (I.3) we have introduced the quantity p h A kT A A Bo kT kT (B11) related to the Boltzmann factor of nucleus A.
Using (B8) and (B14) in this particular case we get: M zA d d 22 d33 d 44 4 M oA 11 2 2 2 2 p 2 M oA d11 d 22 d33 d 44 p (B15) In the x direction I xA 0 1 1 2 0 0 1 0 0 0 0 0 0 1 0 0 1 0 (B16) and the "recipe" leads to .Density Matrix Formalism 125 d11 D d 21 d31 d 41 where d kj d12 d 22 d 32 d 42 d13 d 23 d 33 d 43 d * ). We have for instance I zA 1 1 0 2 0 0 0 1 0 0 0 0 1 0 0 0 0 1 (B14) in which only four matrix elements out of 16 are nonvanishing. jj d14 d 24 d34 d 44 d * and djj = real ( d jj jk The angular momentum components for the AX system are given in (C12) through (C15).
the transverse magnetization MT This leads to the simplified form M x iM y (B19) M TA 4 M oA d *12 d *34 p 2 M oX d11 d 22 d33 d 44 q 4 M oX d *13 d *24 q (B20) The magnetization components for the other nucleus of the system. We denote with m the phase of the complex quantity cm: cm cm exp(i m ) (B24) A nondiagonal matrix element is . are given by M zX M TX (B21) (B22) This is equivalent to calculating the trace (sum of diagonal elements) of the product I D : I nm d mn Tr ( I D) (B23) n m The density matrix at thermal equilibrium At equilibrium the nondiagonal elements are null because of the random phase distribution of the complex coefficients cm.126 Appendix B M xA 2 M oA d *12 d *21 d *34 d *43 p 2i M oA d *12 d *21 d *34 d *43 p (B17) In the same way we obtain M yA (B18) It is always convenient to combine Mx and My in one complex quantity. nucleus X.
. . 0 . The average of a multitude of such vectors is null. The diagonal elements are not null since m m= 0. 0 0 . . . may be oriented in any direction. . . PN (B27) where Pn 1 (normalized populations). . therefore dmm = Pm is the population of this state.f. . d mm In quantum mechanics cm 2 * cm cm cm 2 (B26) is the probablity of finding the system in the state m . described as a vector in the complex plane. The complex number exp[i( m n)].Density Matrix Formalism 127 d mn * cm cn cm cn exp i ( m n ) (B25) The phase difference m n can have any value within 0 and 2 with equal probability. Evolution of the density matrix between pulses In the absence of the r. . The density matrix at equilibrium is P 1 0 D . 0 0 P2 . excitation the Hamiltonian H accepts the kets n as eigenfunctions: H n and the Schrödinger equation En n (B28) i becomes: t H . . . .
This gives cn (0) exp(C ) and (B35) becomes cn cn (0) exp iEn t (B36) Knowing the evolution of all cn coefficients will allow us to predict the time variation of the density matrix. (B30) is satisfied only if each term of the sum is null: cn En Hence dcn i dt 0 (B31) 1 dcn cn dt or iEn (B32) d ln cn dt Integrating (B33) yields: iEn (B33) ln c iEn n t C (B34) cn exp iEn t exp(C ) (B35) The integration constant C may be related to the value of cn at time t 0 .128 Appendix B i Rearranging (B29) gives dc n n dt dcn i dt cn En n (B29) cn En n 0 (B30) Due to the orthogonality of the eigenfunctions. hence that of the magnetization: .
First. For comparison.f. the Hamiltonian in the rotating frame is H BI z (B39) while in the laboratory frame it has the expression H Bo I z (B40) . as we did in the previous section. This problem can be circumvented by describing the evolution of the system in a rotating frame. Effects of radiofrequency pulses We have to find the time evolution of the density matrix under a given Hamiltonian. while the main magnetic field Bo is replaced by B Bo tr The resultant of B1 and B is the effective field Beff (Figure B. in which the rotating magnetic field appears as an immobile vector B1. The Hamiltonian in the rotating frame is then H B1 I x (B38) as we have assumed that B1 is applied along the x axis of the rotating frame. The populations are invariable because Em Em= 0 (relaxation processes are neglected throughout this book). field. but there are two things that make the problem more complicated.Density Matrix Formalism 129 d mn * cm cn * cm (0) cn (0) exp i Em En t (B37) d mn (0) exp( i mn t) We have demonstrated here the relation (I. the Hamiltonian is now timedependent (radiofrequency magnetic field). in the absence of the r. The field B1 is usually much larger than B and the effective field practically is B1.1).13) used in the density matrix treatment to describe the evolution between pulses.
We have to use a more general equation which describes the evolution of D under any Hamiltonian: dD dt i ( DH H D) (B41) the demonstration of which is given separately in the following section.130 Appendix B z B =Bo  tr /  y Beff B1 x Figure B.1. tr = angular frequency of r. The effective magnetic field Beff in the rotating frame. Ox. Oy = axes of the rotating frame . The solution of (B41) is: D(t ) exp iH t / D(0) exp iH t / (B42) This can be verified by calculating the time derivative of (B42): .f. transmitter (angular velocity of the rotating frame) Now we come to the second difficulty which prevents us from using the same approach as in the previous section: the new Hamiltonian (B38) does not have the kets n as eigenfunctions because we have passed from B0 to B1.
D(0) and D denote the density matrix before and after the pulse. according to (B38): iH t / where i B1 I x t i Ix (B43) B1t is the rotation angle of the magnetization around B1 D exp iI x 1 in the time t (pulse duration). In order to get an explicit matrix expression for R we have to calculate R x exp(i I x ) (B45) using a series expansion of the exponential [see(A11)]. We have thus demonstrated the relation (I.f. field B1 applied along the x axis of the rotating frame we have. 3! (B46) The powers of Ix may easily be calculated if one notices that .8). R x 1 i Ix (i ) 2 I x 2 2! (i )3 I x 3 ... Relation (B42) becomes D(0) exp iI x (B44) R D(0) R where R is the rotation operator [cf (A6)(A7)].Density Matrix Formalism 131 dD dt d exp dt exp exp iH t / D(0) exp iH t / iH t / iH t / dD(0) exp iH t / dt d D(0) exp iH t / dt iH exp iH t / iH t / D(0) exp iH t / D(0) iH exp iH t / i/ 0 exp iH / D D iH / DH H D In the particular case of a strong r.
4! ( / 2)5 ...132 Appendix B I x2 1 4 1 (B47) Ix 1 0 1 2 1 0 1 1 0 4 0 1 1 0 1 8 1 0 1 1 4 1 2I x 8 1 1 16 1 2n 1 2n 1 (B48) I x2 1 Ix 4 3 Ix I x4 1 1 0 16 0 1 1 1 0 2n 0 1 1 0 1 2n 1 0 In general. Introducing (B48) and (B49) in (B46) and separating the even and odd terms gives: R x 1 ( / 2) 2 2! ( / 2)3 3! ( / 2) 4 .. 5! 1 0 0 1 0 1 1 0 i /2 (B50) Recognizing the sine (A12) and cosine (A13) series expansions we can write . for n = even we have: I xn and for n = odd I xn 2I x (B49) By using (C12) and (C14) one can verify that (B48) and (B49) are also true for IxA and IxX in a two spin system with I=1/2..
If the radiofrequency field B1 is applied along the x axis. The reader may check some of those results by making = 90o or = 180o in the relations above. it has the same effect as a pulse along the +x axis. (B49) apply: n Iy 1 2n 1 2n 1 for n=even (B53) n Iy (2 I y ) for n=odd and we obtain R y exp(i I y ) cos 2 [1] i sin 2 (2 I y ) (B54) Appendix C contains angular momentum components and rotation operators in matricial form. only the sense of . relations similar to (B48). for a variety of spin systems and pulses.Density Matrix Formalism 133 R x cos cos 0 2 2 1 0 0 1 0 cos 2 i sin 2 0 0 1 1 0 cos 2 1 i sin 2 2I x i sin 2 0 2 cos 2 2 i sin cos 2 (B51) 2 i sin i sin For nucleus A in an AX system the rotation operator is cos i sin R x 2 2 i sin cos 0 0 2 2 0 0 cos i sin 2 2 0 0 i sin cos 2 2 0 0 (B52) If the pulse is applied along the y axis.
y) and/or off resonance pulses (Beff does not coincide with B1). x. Demonstratiom of (B41) In order to demonstrate that dD dt i ( DH H D) we follow the procedure used by Slichter (see Suggested Readings). as shown in the second part of the book. it is more convenient to handle them by means of the Product Operator formalism (see Appendix M). The result of such a pulse is therefore a rotation by around Ox : R ( x) R( )x exp( i I x ) cos 2 [1] i sin 2 (2 I x ) (B55) It is possible to extend the DM treatment to pulses with any phase (not only the four cardinal phases x. y. We start with the (time dependent) Schrödinger equation i where t N H cn n n 1 with the observation that n are not assumed to be eigenfunctions of H. We will not discuss them here because.134 Appendix B rotation is reversed (left hand instead of right hand rule). Combining the last two equations gives N i n dc n n 1 dt N cnH n n 1 (B56) If we premultiply this equation with the bra m we get .
so (B57) becomes dc n i dt If we consider now the product N cn H mn n 1 (B59) p jk its time derivative will be * c j ck (B60) dp jk dt dc j dt c * k * dck cj dt dc j dt i N c * k cj dck dt i * N * cn H jn c n 1 * k cj N cn H kn n 1 i N * * c j cn H kn n 1 * cn ck H jn n 1 The change of sign comes from ( i)* = i. If we take into account that H is Hermitian (H*kn = Hnk) we get .Density Matrix Formalism 135 N i n dc n mn 1 dt N cn m H n n 1 (B57) The choice of normalized and orthogonal functions for the basis set n implies mn mn 0 1 for m n (B58) for m n On the other hand m H n is the matrix element Hmn in the matrix representation of the Hamiltonian.
.136 Appendix B dp jk dt i N N p jn H nk n 1 n 1 H jn pnk (B61) The density matrix element djk is nothing other than the product pjk averaged over the whole ensemble: d jk p jk On the other hand the Hamiltonian and its matrix elements are the same for all the systems within the ensemble. they are not affected by the operation of averaging. so (B62) can be written as dD dt i jk DH jk HD i jk DH H D jk This demonstrates (B41) since the time derivative of a matrix is performed by taking the derivative of each element. Taking the average on both sides of (B61) yields dd jk dt i N N d jn H nk n 1 n 1 H jn d nk (B62) According to the matrix multiplication rule (see Appendix A) the sums in (B62) represent matrix elements of the products DH and HD.
R 2 2 2 2 y (C3) i sin sin 1 2 R90 x 1 1 i 2 i 1 0 i i 0 R90 y 1 1 1 1 0 1 1 0 (C4) R180 x .Angular Momentum and Rotation Operators 137 APPENDIX C: ANGULAR MOMENTUM AND ROTATION OPERATORS System (spin): A(1/2) Ix 1 0 1 2 1 0 1 1 2 0 cos 0 1 i sin cos . I x iI y 2 0 0 1 0 0 0 (C7) . I x iI y 0 1 0 0 cos sin cos (C2) R 2 2 2 2 . R180 y (C5) System (spin): A(1) Ix 0 1 0 1 1 0 1 2 0 1 0 1 Iz 0 0 0 0 0 0 0 1 . x . Iy 1 0 2 i i 0 (C1) Iz . Iy 0 1 i 2 0 i 0 i 0 i 0 (C6) 0 1 0 .
R90 y 1 2 0 2 1 0 1 R180 x 0 1 . R180 y 0 1 (C11) System (spin): A(1/2) X(1/2) I xA 0 1 0 0 1 1 0 0 0 2 0 0 0 1 0 0 1 0 1 1 0 2 0 0 0 1 0 0 0 0 1 0 0 0 0 1 .( I x iI y ) A 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 0 (C13) .138 Appendix C R x cos 1 i 2 sin 1 i 2 sin 2 cos 2 cos 1 i 2 sin 1 cos 2 sin 2 cos 2 sin cos i 2 sin cos 1 (C8) 1 1 cos 2 sin 1 cos 1 2 2 1 0 0 1 0 (C9) R y 1 2 2 sin 1 cos 1 1 R90 x i 2 1 2 (C10) 1 1 i 2 0 i 2 2 1 i 2 1 0 0 1 0 1 0 0 . I yA 0 1 i 2 0 0 i 0 0 0 0 0 0 i 0 0 i 0 (C12) I zA .
2 i 0 1 0 0 i 0 1 . R90 yA 1 1 1 2 0 0 1 1 0 0 0 0 1 1 0 0 (C16) 1 1 1 i 1 0 0 2 0 0 1 i 0 0 i 1 0 R180 xA i 0 0 R180 yA 0 1 0 0 1 0 0 0 0 0 0 1 0 0 (C17) 1 0 i 0 0 0 .Angular Momentum and Rotation Operators 139 I xX 0 0 1 1 0 0 0 2 1 0 0 0 1 0 0 1 0 0 .( I x i I y ) X 0 0 1 0 0 0 0 1 0 0 0 0 0 0 0 0 (C15) 1 R90 xA i 0 0 . I yX 0 1 0 2 i 0 0 0 0 i i 0 0 0 0 i 0 0 (C14) I zX 1 1 0 2 0 0 0 1 0 0 0 0 1 0 0 0 0 1 . 0 0 0 i 0 0 i 0 1 0 R90 xX i 0 R90 yX 1 1 0 2 1 0 0 1 0 1 1 0 1 0 0 1 (C18) 0 1 1 0 1 0 i .
140 Appendix C R180 xX 0 0 i 0 0 0 0 i i 0 0 0 0 i 0 0 . R90 y (13) 1 2 1 0 1 0 0 2 0 0 1 0 1 0 0 0 0 2 (C22) . R180 y (24) 1 0 0 0 0 0 0 1 0 0 1 0 0 1 0 0 (C21) 1 R90 x (13) 1 2 0 i 0 0 2 0 0 i 0 1 0 0 0 0 2 . affecting only one of the two possible transitions of nucleus X: 24 or 13. 2 R90 x (24) 1 2 0 0 0 0 1 0 i 0 0 2 0 0 i 0 1 . R180 yX 0 0 1 0 0 0 0 1 1 0 0 0 0 1 0 0 (C19) Examples of selective rotation operators. R90 y (24) 1 2 2 0 0 0 0 1 0 1 0 0 2 0 0 1 0 1 (C20) R180 x (24) 1 0 0 0 0 0 0 i 0 0 1 0 0 i 0 0 .
System (spin): A(1) X(1/2) The energy states are labeled according to the figure below. R180 y (13) 0 0 1 0 0 1 0 0 1 0 0 0 0 0 0 1 (C23) Selective rotation operators for the nucleus A (transition 12 or 34) can be written in a similar manner. E1 1 1/2 A E2 0 1/2 A X X E3 1 1/2 X 1 1/2 E4 A 0 1/2 E5 A 1 1/2 E6 I xA 0 0 1 1 2 0 0 0 0 0 0 1 0 0 1 0 0 0 1 0 0 1 0 0 0 1 0 0 1 0 0 0 0 0 0 1 0 0 (C24) .Angular Momentum and Rotation Operators 141 R180 x (13) 0 0 i 0 0 i 0 1 0 0 0 0 0 0 0 1 .
. 1/2) system: 1 0 R90 yA 1 2 2 0 1 0 0 1 0 2 0 1 2 0 1 0 2 0 0 2 0 1 0 2 1 0 2 0 1 0 0 1 0 2 0 1 (C26) R180 xX 0 i 0 0 0 0 i 0 0 0 0 0 0 0 0 i 0 0 0 0 i 0 0 0 0 0 0 0 0 i 0 0 0 0 i 0 (C27) Reciprocals R 1 of all rotation operators can be found through transposition and complex conjugation (see Appendix A). Examples of rotation operators for the AX(1. taking (C6) and (C1) as starting points.142 Appendix C I xX 0 1 1 0 2 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 1 0 (C25) Iy can be written in the same way.
Angular Momentum and Rotation Operators
143
Rotations about the zaxis These rotation operators are needed in the following section (Phase Cycling). They can be derived in the same way as the x and y rotation operators [see (B45) to (B54)], after observing that
I zn
1 2n 1 2n
1
for n=even
I zn
(2 I z )
for n=odd
(C28)
For the one spin system A(1/2) we have
R
with
z
b 0
0 b*
(C29)
b cos( / 2) i sin( / 2) exp(i / 2)
For the two spin system A(1/2)X(1/2) we have
(C30)
R
zA
b 0 0 0
0 b* 0 0
0 0 b 0
0 0 0 b*
b2
; R
zX
b 0 0 0
0 0 1 0 0 0 0 b *2
0 b 0 0
0 0 0 0 (C31) b* 0 0 b*
0 1 0 0
R
zAX
R
zA
R
0
zX
0 0
(C32)
144
Appendix C
Phase cycling This section contains rotation operators for phase cycled pulses. The rotation axis for such pulses is situated in the xy plane and makes an angle with the xaxis. In succesive runs, the angle assumes different values. When is equal to 0o, 90o, 180o, or 270o, the rotation axis is x, y, x , or y , respectively. The expressions given in this section are valid for any value of , even if it is not a multiple of 90o. Such values are seldom used in pulse sequences but they may be used to assess the effect of imperfect phases. The rotation operator R90 represents a 90o rotation about an axis making the angle with the xaxis. In order to find the expression of R90 , we observe that this rotation is equivalent with the following succession of rotations: (clockwise) about Oz, bringing the a. A rotation by rotation axis in line with Ox. b. A 90o rotation about Ox. c. A rotation by (counterclockwise) about Oz. For the onespin system A(1/2), using (C29), this leads to
R90 b* 0
1 b* 2 0
where b
R(
)z
R90 x R b 0
z
0 b
b ib
1 1 i 2 i 1
ib * b*
0 b*
ib *2 1
(C33)
0 b
1 1 2 ib 2
exp(i / 2) from (C30). With the new notation
a ib *2 i exp( i )
(C34)
the relation (C33) becomes
R90
1 2
1 a*
a 1
(C35)
In a similar way one can demonstrate that
Angular Momentum and Rotation Operators
145
R180
0 a*
a 0
(C36)
For the twospin system A(1/2)X(1/2)
R 90
A
1 2
1 a* 0 0
a 1 0 0
0 0 1 a*
0 0 a 1
(C37)
R 90
X
1 2
1 0 a* 0
0 1 0 a*
a 0 1 0
0 a 0 1
(C38)
1 R 90
AX
a 1 1 a*
a 1 1 a*
a2 a a 1
(C39)
R 90
A
R 90
X
1 2
a* a* a *2
This operator has been used in the DM treatment of INADEQUATE [see (I.83)]. One can verify that for = 0 we have a = i and R 90 AX R90 x AX [cf.(I.34)] When = 90o we have a = 1 and
R 90
AX
R90 y AX
[cf.(I.101)]
146
Appendix C
For the 180o pulse, similar calculations lead to
R180
A
0 a* 0 0 0 0 a* 0
0
a 0 0 0
0 0 0 a*
a 0 0 0
0 1 0 0
0 0 a 0 0 a 0 0
a2 0 0 0
(C40)
R180
X
0 0 0 a*
0 0 1 0
(C41)
R180
0
AX
0 a *2
(C42)
The 180o operators can be calculated by multiplying the respective 90o operator with itself (two successive 90o rotations). Cyclops Even in the simplest onedimensional sequences, involving one single pulse (the "observe" pulse), a form of phase cycling is used in order to eliminate the radiofrequency interferences. The observe pulse is cycled through all four phases, e.g. clockwise: +x, y, x, +y. The f.i.d. phase follows the same pattern. There will be no accumulation unless the reciever phase is also cycled clockwise. An extraneous signal is not phase cycled and it will be averaged out because of the receiver cycling, provided the number of transients is a multiple of four. The procedure is known as "cyclops".
There is also only one nonvanishing element per column. therefore its trace is equal to N. The nonvanishing elements of a PO are either 1 or i . cL PL 1 where L N2 (D2) . 1. any N N matrix can be expressed as a linear combination of PO's : D c1 P c2 P2 . 3. Properties 1 and 2 are found in the matrices representing angular momentum components Ix. Iz (see Appendix C).. The product of two different PO's is traceless. A product of two matrices having these properties inherits them. The square of a given PO is equal to the unit matrix. The basis set for this system consists of N2 product operators (PO) which are N N hermitian matrices. There is only one nonvanishing element per row. Iy.Properties of Product Operators 147 APPENDIX D: PROPERTIES OF PRODUCT OPERATORS A system of m spin 1/2 nuclei has N = 2m states. the trace (sum of diagonal elements) of their product is Tr( Pj Pk ) djk = 0 djk = 1 N jk (D1) where djk (the Kronecker delta) has the value k if j if j = k The property (D1) illustrates the orthogonality of the PO's. any PO has only N nonvanishing elements out of N2 elements. 4. We summarize here the most significant features of these matrices.. If Pj and Pk are two product operators from the basis set. 2. As a consequence. Expressing a given matrix in terms of PO's Since the basis set is a complete set.
1 . . . . i . . . . At the end of this appendix a computer program can be found (written in BASIC) which can help generate all the product operators for n = 2. i . . 1 . . the coefficients cj can be determined using the orthogonality relation (D1). For the same reason. m m Tr( DPj ) k 1 ck Tr( Pk Pj ) k 1 ck N kj Nc j (D3) Therefore cj 1 Tr( DPj ) N (D4) In the PO treatment of NMR sequences we do not have to go through the routine described above since we start with the density matrix expressed in terms of PO's and we have rules for any rotation or evolution which give the new density matrix also expressed in terms of PO's. . . . . . i . . . . . . . . 1 . . . . . [11 y ] . we do not need to know the PO's in their matrix form in order to operate with them. . . . i . . . . . . . . . . . i . .148 Appendix D Given the matrix D. . We give in the following pages a few examples of PO's in matrix form for m = 3 (N = 8) and for m = 4 (N = 16). . 3. . . [111] . i . . . . . . . . . . . . 1 . . 1 . . . . . or 4. . . . . . . 1 .1. . . . . . . . . . . In all the matrices given below as examples. the dots represent zeros. . . . . . . . . . . . . . 1 . . . . . i i . . . . . . The complete basis set for m = 2 (N = 4) is given in table II. 1 .
. . . i . . . . i . . . . . . 1 . i . . . . . . 1 . . . i . . . . . . . i . . . . . . . . . . . . . 1 . . . . . . i . . . . . . i . . . . . . . . . 1 . . i . . [ x1 y ] . . . . . . i . . 1 . . . . . . . . . . . . . . i . . i . . . [ z11] . . . . . . . . . . . . . . . . . . . . . . i . . . . . i . . . . . . . . i . . . i . . . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . i . . . . . . . . . . . . . . . i . i . . . . . . [1 xy ] . 1 . . . . . i . 1 . . . . . . . . . . . i . . . [1 xx ] . . i . i . . . . . . . . . . . . . . . 1 [1 y1] . . . . . . . i . . . . . i . . . . 1 . . . . . . . . . . [ zxy ] . . . i . . . i . . . . . . . [ xy1] . . . . . i . . . . . . . . . 1 . . . . i . . . . . . i . . . . . . . . . . . . . i . . . . . i . . . . i . . . 1 . i . i . . . 1 . . i . . . . . . . . . . i . . . . . . . . . . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . i . . . . . i . i . . 1 . 1 . . . . . [ xyz ] . . . . . . i . . . . . . . . . . . . . 1 . . . i . i . . . i . . . . . . . .Properties of Product Operators 149 1 . . . i . i . . . . . . . . . . . . i . . . . . . . . . . . . . . .
. . . . . . . 1 . . . . . 1 . . . . . . . 1 . [1 zy ] .150 Appendix D . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . 1 . . . . i . . . . . . . 1 . . . . . . . . . . . i . [ yxy ] . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . i . . . i . . . . . . . . . . . . . . . . . . i . . . . . . i i . 1 . . 1 . . . i . . . . . . . . i . . . . . 1 . i i . . . . . . i . . . 1 . . . . . i . . . i . . . . . . . . . . . . . . . . . . 1 . . 1 . . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . i . . . [ x111] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i . . . . . . i . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . [ yyy ] . . . i . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . 1 . . i . . . . . . i . . . 1 . . . . . 1 . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [ zzy ] . . . . . . . . 1 . . . . . . 1 . . . . . . . . . . .i . 1 . . . . . . i .
. 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . 1 . . . . . . . . . . . . . . . . . . i . . . . 1 . . . . . . . . . . i . . i . . . . . 1 . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . . . . [ xyz1] . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . i . i . . . . . . . . . . . . . . . . . . .Properties of Product Operators 151 . . . . . . . [1 xx1] . . . . i . . . . . . i . 1 . . . . . i . . . . . . . 1 . . . . . . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i . . . . . . . 1 . . . . . 1 . . . . . i . . . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . i . . . .
. . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . . i . . 1 . . . . . . . . . . . . . . . . . Version CPM86. . . . . . . . . . . . . . . . . . . . . .22 by Microsoft. . . . . . . . . . . . . . . i . . . . . . . . It is written in BASIC. . . . i . . . . . . . . . . . . . . . . . . . . i . . . . . . All the product operators sampled in this appendix have been calculated with the program POP (Product OPerators) listed on the following pages. . . . . . . . . . . . . . i . i . . . 1 . 1 1 . . . . . . . . . . . . i . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . .152 Appendix D . . . . . . . . . . . 1 . . . . . . . . i . . . . . . . . . . . . . i . . . . . . . . . . . . . . [ z1 yz ] . . . . . . . . . [ zzzx ] . . . . . . . . . . . i . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . i . . . i . . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . i . . . 1 . . . . . . . .5. i . . . . . . . . . . . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . Rev. . . . . . . . . . 1 . . . . . . 1 . . . . . . . . . . . . . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . .
Display a specified product operator" 80 PRINT " B .Exit MENU" 120 M%=14 125 FOR I%=1 TO M% : PRINT : NEXT I% 130 INPUT MENU$ 135 IF MENU$="A" THEN GOSUB 4050 137 IF MENU$="B" THEN GOSUB 4000 139 IF MENU$="C" THEN GOSUB 4050 141 IF MENU$="D" THEN GOSUB 4000 143 IF MENU$="E" THEN GOSUB 4500 145 IF MENU$="F" THEN GOSUB 4500 170 PRINT " Do you want to join the MENU again ? (Y or N)" 175 INPUT A$ 180 IF A$="Y" THEN 75 935 END 940 REM.F%(256).Print all product operators (hard copy)" 86 PRINT " E .16).Zero order product operator (unit matrix) 950 FOR M%=1 TO NS% 955 N%(0.Express a matrix in terms of product operators" 88 PRINT " F .M%)=M% 960 D%(O. OR FOUR 13 REM.M%)=1 965 MEXT M% 970 F%(0)=0 .A(16.Properties of Product Operators 153 10 REM.ERNST FOR A SYSTEM OF TWO.NUMBER OF STATES 60 NS%=2^NN% 65 IF NN%=2 THEN B$="14 seconds" 66 IF NN%=3 THEN B$="38 seconds" 67 IF NN%=4 THEN B$="2 min 46 s" 68 PRINT "Please wait ".Print a specified product operator (hard copy)" 84 PRINT " D .J%(4).Same as E but printed (hard copy)" 118 PRINT " X .16) 30 PRINT "NUMBER OF SPIN 1/2 NUCLEI (2.B(16.Subroutine 9403650 to calculate all PO for given NN% 945 REM.BASIC OPERATORS ACCORDING TO SORENSEN12 REM.B$ 70 GOSUB 940 71 REM. THREE.N%(256.SPIN 1/2 NUCLEI 20 DIM D%(256.3.PROGRAM "POP" CALCULATES AND PRINTS THE 11 REM.16).OR 4)" 40 INPUT NN% 45 IF NN%>4 THEN NN%=4 46 IF NN%<2 THEN NN%=2 50 REM.J$(4) 25 DIM B$(256).Display all product operators" 82 PRINT " C .16).All product operators are now calculated and labeled 75 PRINT " M E N U" 76 PRINT " =========" 78 PRINT " A .
M%)=SG% 1060 D%(3*K2%.M%)=1 1050 D%(2*K2.First order product operators Ix.M%)=SG% 1070 M%=M%+1 1080 NEXT C% 1090 SG%=SG% 1100 IF M%<=NS% THEN 1000 1100 NEXT K% 2000 REM.Second order base operators (Two factor PO's) 2010 FOR KA%=1 TO NN%1 2020 FOR KB%=KA%+1 TO NN% 2030 FOR JA%=1 TO 3 2040 FOR JB%=1 TO 4 2050 K2A%=4^(KA%1) 2060 K2B%=4^(KB%1) 2070 SA%=JA%*K2A% : SB%=JB%*K2B% 2080 GOSUB 5000 2090 NEXT JB% 2100 NEXT JA% 2110 NEXT KB% 2120 NEXT KA% 3000 REM.M%)=M%+SG%*K1% 1030 N%(3*K2%.M%)=M% 1040 D%(K2%.M%)=M%+SG%*K1% 1020 N%(2*K2%.154 Appendix D 975 REM. Iz 980 FOR K%=1 TO NN% 985 K1%=2^(K%1) : K2%=K1%*K1% 990 F%(K2%)=0 : F%(2*K2%)=1 : F%(3*K2%)=0 995 M%=1 : SG%=1 1000 FOR C%=1 TO K1% 1010 N%(K2%. Iy.Three factor product operators 3010 IF NN%<3 THEN 3625 3020 FOR KC%=1 TO NN%2 3030 FOR KD%=KC%+1 TO NN%1 3040 FOR KB%=KD%+1 TO NN% 3050 FOR JC%=1 TO 3 3060 FOR JD%=1 TO 3 3070 FOR JB%=1 TO 3 3080 K2C%=4^(KC%1) : K2D%=4^(KD%1) : K2B%=4^(KB%1) 3090 SC%=JC%*K2C% : SD%=JD%*K2D% : SB%=JB%*K2B% 3100 SA%=SC%+SD% 3100 GOSUB 5000 3120 NEXT JB% 3130 NEXT JD% 3140 NEXT JC% 3150 NEXTKB% 3160 NEXT KD% .
). n(s.m.Operator labeling 3630 FOR S%=0 TO NS%^21 3635 GOSUB 3900 3637 NEXT S% 3640 REM.Subroutine 39003045 generates label.Properties of Product Operators 155 3170 NEXT KC% 3500 REM.All product operators are now calculated and labeled 3641 REM. given s 3901 B$="[" 3904 R%=S% 3908 FOR I%=1 TO NN% 3912 J%(I%)=R%4*INT(R%/4) 3916 R%=INT(R%/4) 3920 IF J%(I%)=0 THEN J$(I%)="1" 3924 IF J%(I%)=1 THEN J$(I%)="x" 3928 IF J%(I%)=2 THEN J$(I%)="y" 3932 IF J%(I%)=3 THEN J$(I%)="z" 3936 B$=B$+J$(I%) 3940 NEXT I% 3943 B$=B$+"]" 3945 RETURN 3950 REM.Subroutine 40004040 to output all product operators . given label 3952 P=0 : S%=0 3955 FOR I%=1 TO NN% 3960 IF J$(I%)="1" THEN J%(I%)=0 GOTO 3985 3965 IF J$(I%)="X" THEN J%(I%)=1 GOTO 3985 3970 IF J$(I%)="Y" THEN J%(I%)=2 GOTO 3985 3975 IF J$(I%)="Z" THEN J%(I%)=3 GOTO 3985 3980 P=1 : GOTO 3995 3985 S%=S%+4^(I%1)*J%(I%) 3990 NEXT I% 3995 RETURN 4000 REM.m).Arrays d(s. F(s) and B$(s) are filled 3650 RETURN 3900 REM.Four factor product operators 3510 IF NN%<4 THEN 3625 3520 FOR JC%=1 TO 3 3530 FOR JD%=1 TO 3 3540 FOR JE%=1 TO 3 3550 FOR JB%=1 TO 3560 SA%=JC%+4*JD%+16*JE% 3570 SB%=64*JB% 3580 GOSUB 5000 3590 NEXT JB% 3600 NEXT JE% 3610 NEXT JD% 3620 NEXT JC% 3625 REM.Subroutine 39503995 generates s.
".J$(3) 4080 IF NN%=4 THEN INPUT J$(1). e.Z. given s 4160 PRINT : PRINT B$(S%)+" =" : PRINT 4166 IF MENU$="C" THEN 4167 ELSE 4170 4167 LPRINT : LPRINT B$(S%)+" =" : LPRINT 4170 FOR M%=1 TO NS% 4180 FOR I%=1 TO N%(S%.156 Appendix D 4005 IF MENU$="D" THEN MENU$="C" 4010 FOR S%=0 TO NS%^21 4020 GOSUB 4155 4030 NEXT S% 4040 RETURN 4050 REM.Y. 4240 FOR I%=N%(S%.X.X." 4055 PRINT B$ 4056 PRINT " then press RETURN" 4060 IF NN%=2 THEN INPUT J$(1). 4235 IF MENU$="C" THEN 4236 ELSE 4240 4236 LPRINT D$. 4195 IF MENU$="C" THEN 4196 ELSE 4200 4196 LPRINT " .Z or 1. 4260 NEXT I% 4265 PRINT 4266 IF MENU$="C" THEN LPRINT ELSE 4270 4270 NEXT M% : PRINT : PRINT 4272 IF MENU$="C" THEN 4273 ELSE 4275 4273 LPRINT : LPRINT . 4052 IF NN%=2 THEN B$="X." 4054 IF NN%=4 THEN B$="X.J$(2) 4070 IF NN%=3 THEN INPUT J$(1).M%)1 4190 PRINT " . ".Y etc.J$(2).Y or 1.Subroutine 41554275 to display or print on PO.Z or X.M%)=1 TO NS% 4250 PRINT " .J$(2).Y. 4200 NEXT I% 4210 D%=D%(S%.g. 4255 IF MENU$="C" THEN 4256 ELSE 4260 4256 LPRINT " .Y.J$(4) 4090 GOSUB 3950 4095 IF P>0 THEN 4105 4100 GOSUB 4155 : GOTO 4107 4105 PRINT : PRINT : PRINT "Please try again " 4107 PRINT "Do you want another ? (Y or N)" 4108 INPUT A$ : IF A$="Y" THEN 4050 4110 RETURN 4155 REM.Z etc.1 etc.M%) 4220 GOSUB 5300 4230 PRINT D$.Subroutine 40504110 to output one specified PO 4051 PRINT "Please label desired product operator." 4053 IF NN%=3 THEN B$="X.".".J$(3).".
")*"B$(S$) 4780 NEXT S% .B 4640 NEXT N% : NEXT M% 4645 PRINT : PRINT : PRINT "Your matrix =" 4646 IF MENU$="F" THEN 4647 ELSE 4650 4647 LPRINT : LPRINT : LPRINT "Your matrix =" 4650 FOR S%=0 TO NS%^21 4660 R%=1F%(S%) 4665 CR=0 : CI=0 4670 FOR M%=1 TO NS% 4680 N%=N%(S%.N%).M%) 4700 CI=CI+(B(M%."N%")=".Subroutine 45004790 to express a given matrix 4501 REM.Properties of Product Operators 157 4275 RETURN 4400 PRINT "Do you want another ? (Y or N)" : INPUT H$ 4410 IF H$="Y" THEN 4002 4500 REM.N%). n.N%.B$.N%)*R%+B(M%.B$. a.A.B$.B$. b then press RETURN" 4569 FOR I%=1 TO N 4570 INPUT M%.N%%)*F%(S%))*D%(S%.B. A(M%.N%) 4626 IF B<0 THEN B=B : B$="i*" 4630 PRINT "d("M%"."N%")=".N%%)*F%(S%))*D%(S%. A(M%.B 4635 IF NEMU$="F" THEN 4636 ELSE 4640 4636 LPRINT "d("M%".B 4580 A(M%.N%)*R%A(M%.N%)=A : B(M%.N%)=0 THEN 4640 4625 B$="+i*" : B=B(M%.M%) 4690 CR=CR+(A(M%.M%) 4710 NEXT M% 4720 CR=CR/2 : CI=CI/2 4730 IF CR=0 THEN IF CI=0 THEN 4780 4735 B$="+i" : B=CI 4736 IF CI<0 THEN B=B : B$="i*" 4740 PRINT "("CR.N%)=B 4590 NEXT I% 4600 T$="Your matrix has the following nonzero elements" 4601 PRINT T$ 4601 IF MENU$="F" THEN LPRINT T$ 4610 FOR M%=1 TO NS% : FOR N%=1 TO NS% 4620 IF A(M%.B.N%)=0 THEN IF B(M%.in terms of product operators 4530 FOR M%0 TO NS% : FOR N%=0 TO NS% 4540 A(M%.N%)=0 : B(M%.")*"B$(S$) 4745 IF MENU$="F" THEN 4746 ELSE 4780 4746 LPRINT "("CR.N%)=0 4550 NEXT N% : NEXT M% 4555 PRINT "How many nonvanishing elements in the matrix ?" 4556 INPUT N 4560 PRINT "For every nonvanishing element in your matrix" 4561 PRINT " d(m.n) = a + i*b" 4562 PRINT "please enter: m.
MB%) 5050 D%(S%.Subroutine 50005090 special matrix multiplication 5010 S%=SA%+SB% 5020 FOR M%=1 TO NS% 5030 MB%=N%(SA%.M%)*D%(SB%.MB%)5060 NEXT M% 5070 F%(S%)=F%(SA%)+F%(SB%) 5080 IF F%(S%)>1 THEN GOSUB 5100 5090 RETURN 5100 F%(S%)=0 5110 FOR M%=1 TO NS% 5120 D%(S%.M%)=D%(SA%.M%) 5122 NEXT M% 5130 RETURN .M%)=N%(SB%.158 Appendix D 4781 PRINT : PRINT 4790 RETURN 5000 REM.M%) 5040 N%(S%.M%)=D%(S%.
We start from the rotation operator applied to a density matrix and we make use of the commutation rules for the operators Ix.6 (correspondence between the vector rotations and the PO formalism). Iy. which are: IxI y I yIz Iz Ix I y Ix Iz I y IxIz iI z iI x iI y (E2) It is necessary to emphasize that the above rules apply not only to an isolated spin but also to every particular nucleus in a multinuclear system (with or without coupling). For instance: I xA I yM I xA I xM I yM I xA I xM I xA 0 0 (E3) The rotation operator R x [see(B45)] has the expression: R x exp(i I x ) R 1 D ( n) R x (E4) Applied to a density matrix D(n) it will yield: D(n 1) x (E5) . In an AMX system for instance we have for nucleus A: I xA I yA I yA I xA iI zA (and so on) Angular momentum components of different nuclei within a system are commutative. Iz.Demonstration of the Rotation Rules 159 APPENDIX E: DEMONSTRATION OF THE ROTATION RULES We demonstrate here the validity of the PO pulse rotations derived from the vector representation in Section II. Demonstration of an x rotation We will demonstrate an rotation around the xaxis: Iy x I y cos I z sin (E1) Other rotations can be demonstrated in a similar way.
To demonstrate (E8) we postmultiply the first relation in (E2) by I x and. taking (B48) into account. we get D(n 1) cos which confirms (E1). so what we have to demonstrate is: D(n 1) 1 R xIyR x I y cos I x sin (E6) In Appendix B we have demonstrated [see (B51)] that R x cos 2 [1] i sin 2 (2 I x ) (E7) Introducing this expression in (E6) gives D(n 1) cos 2 [1] i sin 2 (2 I x ) I y cos 2 [1] i sin 2 (2 I x ) cos 2 2 Iy 4sin 2 2 IxI yIx 2i cos 2 4sin 2 (I y I x IxI y ) After using the first relation in (E2) this becomes D(n 1) cos 2 2 Iy 4sin 2 2 IxI y Ix 2i cos 2 4sin 2 ( iI z ) cos 2 2 Iy 4sin 2 2 I x I y I x sin 1 Iy 4 I y sin Iz Iz If we use now the relation IxI yIx (E8) which will be demonstrated immediately. we obtain IxI yIx 1 Iy 4 iI z I x (E9) Premultiplying of the first relation in (E1) by Ix yields 1 Iy 4 IxI yIx iI x I z (E10) .160 Appendix E In (E1) we have assumed that D(n) is equal to Iy.
What we have to calculate is: D(n 1) exp( i I xA ) 8 I yA I zM I yX exp(i I xA ) (E11) We have stated (E3) that IxA commutes with both IzM and IyX. M. The latter is a shorthand notation for the product.Demonstration of the Rotation Rules 161 Subtracting (E10) from (E9) gives 2I x I y I x or 1 Iy 2 i( I z I x I x I z ) i (iI y ) Iy 2I x I y I x which demonstrates (E8). Since these subscripts are omitted for simplicity in the product operator label [yzy]. X refer to the different nuclei in the system. 1 Iy 2 Rotation operators applied to product operators Suppose we have to apply the rotation operator the R xA to the product operator [yzy]. Using (E6) we get: D(n 1) 8(cos In shorthand notation: I yA sin I zA ) I zM I yX [ yzy ] xA [ yzy ]cos [ zzy}sin (E12) This can be phrased as follows: A rotation operator affects only one factor in the product operator and leaves the others unchanged. This enables us to rewrite (E11) as: D(n 1) exp( i I xA ) I yA exp(i I xA )8I zM I yX and we have reduced the problem to a known one. X. M. (2 I yA )(2 I zM )(2 I yX ) The subscripts A. . The affected factor parallels the vector rotation rules. we have to keep in mind as a convention that the different nuclei of the system appear in the product operators always in the same order: A.
The result (E13) may seem unexpectedly complicated for one single pulse. In such cases. We have sometimes to handle nonselective pulses. The procedure described above has to be followed even if the spins affected by the pulse are magnetically equivalent.162 Appendix E This is true in the case of a selective pulse. Fortunately. the procedure above leads to exhilariatingly simple results like: [ yzy ] [ yzy ] [ xyz ] 90 xMX 180 xMX 90 xAM [ yyz ] [ yzy ] [ xzz ] In these cases it is not necessary to split the nonselective pulse into subsequent selective pulses. affecting two or more nuclei in the system. in most practical cases is either 90o or 180o. The problem [ yzy ] has to be handled as xX xMX [ yzy ] xM [ yzy ]cos 2 [ yzy ]cos [ yyy ]sin [ yzz ]cos sin [ yyz ]sin 2 (E13) [ yyy ]sin cos The reader can easily check that the order in which xM and xX are applied is immaterial. not in the hardware) the nonselective pulse by a sequence of selective pulses following immediately one after another. In these cases. . the procedure to follow is to substitute (in the calculations.
Demonstration of the Coupled Evolution Rules 163 APPENDIX F: DEMONSTRATION OF THE COUPLED EVOLUTION RULES Before going into the demonstration we need to point out two limitations: a.f. It operates in the weak coupling case: (chemical shift difference) J (coupling constant)<< Between r. we can write the evolution operator as: exp iH t / exp i A tI zA exp i X tI zX exp i 2 JtI zA I zX RA RX RJ where the order of the factors is immaterial. shift X. Example: [ xy ] X A t [ xy ]cos [ xy ]cos [ yy ]sin A A t [ yy ]sin X A t t sin At sin A t t cos At cos t [ xx]cos X t [ yx ]sin t Xt X . and coupling J. Relation (F2) can be rewritten as: (F3) D(n 1) RJ 1 RX1 RA1 D(n) RA RX RJ In (F3) the actual coupled evolution is formally presented as the result of three independent evolutions due to shift A. The shift evolutions (noncoupled evolutions) are actually zrotations and are easily handled with the vector rotation rules. In fact this is the way the coupled evolutions are handled in the PO formalism: as a succession of shift evolutions and evolutions due to spinspin coupling (coupling evolutions). respectively. H 2 JI zA I zX (F1) A I zA X I zX The density matrix D(n+1) at the end of the evolution is related to the initial matrix D(n) as: D(n 1) exp( iH t / ) D(n) exp(iH t / ) (F2) Since all terms in (F1) commute with each other. It assumes I=1/2 for all nuclei in the system b. pulses the evolution of a twospin system AX in the rotating frame is governed by the Hamiltonian.
[ xy ] A t X t cc '[ xy ] cs '[ xx] sc '[ yy ] ss '[ yx] (F4) RJ 1 D(n) RJ (F5) The object of this appendix is to derive the rules for calculating D (n 1) where RJ exp i 2 JtI zA I zX and D(n) may be any of the product operators or a combination thereof. all these POs have only diagonal elements and are not affected by any evolution. shift or coupling. with selfexplanatory notations. Calculating the powers of IzAIzX we find I zA I zX I zA I zX and this leads to n n 1 [1] 4n 1 4 I zA I zX 4n for n = even for n = odd (F6) (F7) Jt Jt [1] i sin 4 I zA I zX (F8) 2 2 an expression we can use in calculating D (n 1) RJ 1 D (n) RJ . . [z1]. As a matter of fact. [11] is affected by the coupling evolution. Case 1. Both nuclei A and X participate in the product operator with z or 1. Example: D (n) [ zz ] 2 I zA 2 I zX In this case D(n) commutes with both IzA and IzX and this gives: D (n 1) RJ 1 D(n) RJ D(n) RJ 1 RJ D ( n) None of the POs [zz]. We have to discuss three cases. We have to find first an expression similar to (B51) for the operator RJ. RJ cos It is now the moment to introduce specific product operators for D(n). [1z].164 Appendix F Or.
C2) of the angular momentum components for I=1/2. To calculate the product IzAIxAIzAIzXIyXIzX in (F10) we use the following . we can rewrite the last result as D(n 1) cos 2 Jt Jt 3 4 I xA I yX sin 2 4 I zA I xA I zA I zX I yX I zX 2 2 Jt Jt 2 i cos sin 4 I xA I zA I yX I zX I zA I xA I zX I yX (F10) 2 2 Using (F9) we find out that the last parenthesis in (F10) is null. Both nuclei A and X participate in the product operator with an x or a y.Demonstration of the Coupled Evolution Rules 165 Case 2. Using (F8) to calculate D(n 1) we have D(n 1) cos Jt [1] i sin 2 J cos [1] i sin 2 cos 2 Jt 4 I xA I yX sin 2 2 Jt Jt 2 sin 4 I xA I yX I zA I zX i cos 2 2 Jt 4 I zA I zX (4 I xA I yX ) 2 J 4 I zA I zX 2 Jt 3 4 I zA I zX I xA I yX I zA I zX 2 I zA I zX I xA I yX Since the angular momentum components of A are commutative with those of X [see(E3)]. for I = 1/2. the components of the angular momentum ar anticommutative: IxI y I yIz Iz Ix I yIx IzI y IxIz (F9) The validity of (F9) can be verified on the expressions (C1. Example: D(n) [ xy ] 2 I xA 2 I yX We can demonstrate that this kind of product operator also is not affected by the coupling evolution. In order to do so we have to take into account that.
Only this kind of product operator is affected by the coupling. Example: D (n) [ x1] 2 I xA Calculations similar to those performed in Case 2 lead to: D(n 1) cos Jt Jt [1] i sin 2 2 Jt Jt [1] i sin 2 2 sin 2 4 I zA I zX 2 I xA cos 4 I zA I zX cos 2 Jt 2 I xA 2 Jt 32 I zA I zX I xA I zA I zX 2 8I zA I zX I xA i cos Jt Jt sin 8 I xA I zA I zX 2 2 cos 2 Jt Jt 2 2 I xA sin 2 32 I zA I xA I zA I zX 2 2 Jt Jt i cos sin 8 I xA I zA I zX 8I zA I xA I zX 2 2 . The transition frequencies corresponding to these matrix elements do not contain the coupling J.[yx]. Unlike the POs in Case 1. The product operator exhibits z or 1 for one of the nuclei and x or y for the other nucleus.[xy]. they are affected by the shift evolution (see F4). This is consistent with the fact that all the nonvanishing elements of these POs are doublequantum or zeroquantum coherences. similar to (E8) : I zA I xA I zA ( I xA ) / 4 . I zX I yX I zX ( I yX ) / 4 and we reduce (F10) to D(n 1) cos 2 Jt 4 I xA I yX 2 sin 2 Jt 4 I xA I yX 2 4 I xA I yX D(n) All POs in the subset [xx].166 Appendix F relations.[yy] are not affected by the J evolution. Case 3.
Demonstration of the Coupled Evolution Rules 167 Jt Jt 2 I xA sin 2 2 I xA 2 2 Jt Jt i cos I xA I zA I zA I xA 8I zX sin 2 2 Jt Jt cos 2 2 I xA sin 2 2 I xA 2 2 Jt Jt i cos iI yA 8 I zX sin 2 2 cos Jt (2 I xA ) sin Jt (4 I yA I zX ) cos 2 cos Jt[ x1] sin Jt[ yz ] We have demonstrated that J coupl [ x1] [ x1]cos Jt [ yz ]sin Jt After doing similar calculations for all the POs in this category (i. The effect of the J evolution is a rotation of x (or y) in the equatorial plane by Jt. y by x. The format is: PO after J evolution = cos Jt (former PO) + sin Jt (former PO in which x is replaced by y. we can summarize the following rules for the evolution due to the coupling J AX : a. The coupling evolution operator RJ affects only those product operators in which one of the nuclei A. [x1].[y1]. From Appendices E and F it results that any rotation (r.[1x]. b. In other words.[xz]. every nonvanishing coupling like JAM. Note 1.e. if the density matrix can be expressed in terms of POs at the start of a sequence we will be able to express it as a combination of POs at any point of the sequence. Note 2.. JAX. In systems with more than two nuclei. any x or y in the . in a coupled evolution. z by 1 and 1 by z).. etc.f. while z is replaced by 1 and 1 by z in the new term. JMX.[1y]. Moreover. has to be taken into account separately (the order is immaterial).[yz]. This confirms that the PO basis set is a complete set.X is represented by x or y while the other is represented by 1 or z.[zx].[zy]). pulse) or coupled evolution turns a given PO into a linear combination of POs within the basis set.
[zyx]. the descendents of a PO are to be found only within its own subset. Any z or 1 can only become a z or 1. [yxz]. [zz1]. [yz1]. In the case of N = 4 (two nuclei) the four subsets are: 1) [11]. [x1z]. [zzy] 6) [x1x]. [zxy]. [1xz]. [xxz]. [zyz] 4) [xx1]. [xy1]. [z1x]. . [yx]. [1zz]. [yz] 3) [1x]. [zzz] 2) [x11]. [z1]. [xyz]. [xxy]. [1z1]. [zxx]. [xzz]. [xy]. This leads to a natural separation of the basis set (N2 product operators) into N subsets of N operators each. [yx1]. [zy] 4) [xx]. [y11]. [xz1]. [xyx]. [1yx]. [zxz]. [zzx]. [yzz] 3) [1x1]. [x1y]. [1z]. [1xy]. [1y]. [xz]. [11y]. [yy] In the case of N = 8 (three nuclei) the eight subsets are: 1) [111]. [yxx]. [yzy] 7) [1xx]. [xzy]. [zx]. [z1z]. [yyy] Under a coupled evolution. [11z]. [yyz] 5) [11x]. [1zy]. [yyx]. [yzx]. [z1y]. [1yy]. [y1x]. [zy1]. [y1y]. [xzx]. [y1z]. [1y1]. [zx1]. [y1]. [zz] 2) [x1]. [1yz]. [yxy]. [xyy]. [1zx]. [yy1]. [z11].168 Appendix F product operator can only become an x or y. [zyy] 8) [xxx].
PO Evolution Tables 169 APPENDIX G: PO EVOLUTION TABLES The tables below summarize the effect of a coupled evolution on each of the sixteen POs of an AX system (two spin 1/2 nuclei). coupling J. Second subset (affected by A shift and J coupling) Initial PO F i n a l POs [ x1] cC[ x1] sC[ x1] sC[ y1] cC[ y1] cS [ y1] sS [ y1] sS [ xz ] cS [ xz ] cC[ xz ] sC[ xz ] cS [ yz ] sS [ yz ] [ y1] [ xz ] [ yz ] sS [ x1] cS [ x1] sC[ yz ] cC[ yz ] . while the next columns indicate the newly created POs (including the initial one). A coupled evolution implies three PO operations: shift A. The first column in each table indicates the PO before the evolution. a. First subset (not affected by evolution) Initial PO [11] [11] 0 0 0 F i n a l 0 POs 0 0 0 0 0 [ z1] [1z] [ zz ] [ z1] 0 0 [1z] 0 [ zz ] b. Nevertheles no more than four terms are generated from the initial one: when both shifts are active the coupling is not. shift X.
Third subset (affected by X shift and J coupling) Initial PO F i n a l POs [1x ] [ zx ] [1y] [ zy ] c' C[1x ] s' S [1x ] s' C[1x ] c' S [1x ] s' S [ zx ] s' C[1y] c' S [1y ] c ' C[1y] s' S [1y ] c ' S [ zy ] s' C[ zy ] s' S [ zy ] c' C[ zx ] c' S [ zx ] s' C[ zx ] c' C[ zy ] d. . Fourth subset (affected by A shift and X shift) Initial PO F i n a l POs [ xx ] [ yx ] [ xy ] [ yy ] cc'[ xx ] sc '[ xx ] sc '[ yx ] cc'[ yx ] ss'[ yx ] cs'[ yx ] cs'[ xy ] ss'[ xy ] ss'[ yy ] cs'[ yy ] sc '[ yy ] cc'[ yy ] cs'[ xx ] cc'[ xy ] sc '[ xy ] ss'[ xx ] c s cos sin A A t . c ' cos s' sin X X t t . .170 Appendix G c. C S cos Jt sin Jt t .
nucleus A) and see how RA commutes with R180xA.. RX are shift operators and RAX is the coupling operator. All shift and coupling evolution operators commute with each other. the r.Demonstration of the Refocusing Rules 171 APPENDIX H: DEMONSTRATION OF THE REFOCUSING RULES We demonstrate here the validity of the rules stated in Section II. According to relation (B51) R180 xA exp(i I xA ) cos [1] i sin (2 I xA ) 2 2 2iI xA (H2) A similar expression can be written for the shift evolution operator RA which represents a rotation by = A /2 around the z axis. For two nuclei the string would be: R RA RX RAX R180 RAX RX RA (H1) where RA.8 to handle a refocusing routine: 180 When handling this segment of a sequence in the conventional way we have to subject the density matrix D(n) to a string of operators representing the /2 evolution (shifts and couplings). RA R A exp(i I zA ) cos [1] i sin (2 I zA ) 2 2 (H3) .f. Let us concentrate on one nucleus (e. then again the /2 evolution.g. In order to simplify the expression (H1) we have to find out how they commute with R180. pulse (R180).
172 Appendix H We want to examine the product of the two operators: R180 xA R A 2iI xA cos [1] i sin (2 I zA ) 2 2 Using the anticommutativity of Ix and Iz for I=1/2 stated in (F10) we can rewrite the product as R180 xA R A cos [1] i sin (2 I zA ) 2iI xA 2 2 R( )A R180 xA We notice that R(.)A is the reciprocal of R A since their combined action would leave the density matrix unaffected. Therefore we can write in general R180 A RA On the other hand we have RA1 R180 xA RX R180 xA (H5) R180 A RX (H6) since operators acting on different nuclei always commute. A similar pattern can be followed to demonstrate . We can therefore write R180 xA R A R 1 R180 xA A (H4) and this is the commutation rule we needed. One can check that the rule is the same if instead of R180xA we use R180yA or R180 A (180o rotation about an arbitrary axis in the xy plane). For the last case one has use R180 A R( ) zA R180 xA R zA R180 A R 2 zA cos R180 xA R(2 ) zA 2iI xA cos [1] i sin 2 I zA 2iI xA i sin ( 2iI yA ) R180 xA cos We have used here I xA I zA R180 yA sin iI yA / 2 which is a consequence of (E2) and (F9).
If the 180o pulse is applied on both nuclei A and X. the coupling only is expressed in the final result.Demonstration of the Refocusing Rules 173 R180 A RAX R180 X RAX 1 RAX R180 A 1 RAX R180 X (H7) (H8) With these commutation rules we now can rearrange a string like the one in (H1): R RA RX RAX R180 A RAX RX RA 2 RX R180 A 1 RA RX RAX RAX RX RA1 R180 A 2 R180 A RX Only the shift X is expressed in the final result. while shift A and coupling AX are refocused. Since RX is the shift evolution for /2. 2 RX is the operator for the full delay . This confirms the refocusing rules stated in Section II. . There is no difficulty in extending them to more than two nuclei. the rearranging yields: R RA RX RAX R180 A R180 X RAX RX RA RA RX RAX RAX RX1 RA1 R180 A R180 X 1 RA RX RAX R180 A RAX RX1 RA R180 X 2 RAX R180 A R180 X 2 R180 A R180 X RAX Both shifts are refocused.8.
7.34) to D(5) in (I1). Section 3. We do this here.2) we should carry on the calculations without it. that in order to understand the role of the delay 1 (see Figure I. the expressions for F and G are taken F G d13 (5) d 24 (5) 2 exp[ i F H (te 1 )] (I2) If 1 is not used. taken from (I. We start by writing the density matrix before the combined 90xCH pulse: D(5) 3 0 F* 0 0 2 0 G* F 0 3 0 0 G 0 2 (I1) If we have the delay from (I. the expressions for F and G.174 Appendix I APPENDIX I: SUPPLEMENTARY DISCUSSIONS 2DHETCOR without 1 It is stated in Part I. D(5) R90 xCH 3 iF 1 2i G 2 3i F * 2 iG * 3i F 2 iG 3 iF * 2i G * 3i F 2 iG 3 iF * 2i G * 3 iF 2i G 3i F * 2 iG * . are: F d13 (4) 2i exp( i H te ) G (I3) We apply the operator R90xCH given in (I.26).32): 1 = 1/2J.25) and (I.
this information disappears from the observable singlequantum coherences d12 and d 34. when they are equal. The factors F and G contain the proton information [see (I3)] and. In this case D(7) becomes D (7) 5 iF iF * 2i F F* 0 2i 5 iF iF * 0 F F* 1 F F* 0 5 iF iF * 2i 2 0 F F* 2i 5 iF iF * (I5) .Supplementary Discussions 175 Premultiplication with R 901xCH gives the following expression for D(7) 10 i (F F* G G*) 2i F F* G G* F G F * G* i( F F* G G*) 2i F G F * G* 1 4 F G F * G* 10 i (F G F * G*) i( F G F * G*) F G F * G* i( F G F * G*) 10 i ( F G F * G*) 2i F G F * G* i( F F* G G*) F G F* G* 2i F* F G* G 10 i ( F F* G G*) (I4) Now we can see why having G = F is counterproductive.
9. We will not have a 2D. The DM calculations in Sections 3." The matrix elements d12 and d34. The role of the subsequent coupled evolution 2 is explained in Section 3. i.9 have been carried on with the delay 1 = 1/2J. .e.31) c s we obtain cos[ sin[ H H (te (te 1 1 )] )] F F F 2(c is ) F * 4is F* 4c (I7) By introducing (I7) into (I6) we can verify the expression of D(7) given in (I. In this case D(7) is D(7) 1 2 5 i F F* 0 i( F F *) i F F* 5 i ( F F *) F F* 0 i( F 5 i F F* F *) i( F F *) 0 i F F* 5 (I6) Taking F from (I2) and using the notations (I. will be affected by the carbon evolution during the detection td (preceded or not by the coupled evolution 2) but they will not be proton modulated.176 Appendix I No pulse follows after t(7) and each matrix element evolves in its own "slot. with G = F [see (I2)].35).6 to 3. The carbon observables d12 and d34 contain now the factor s which carries the proton information.
all we have between t(1) and t(5) is an evolution te. The density matrix at t(1). is 2 D (1) 0 2i 0 0 3 0 2i 2i 0 2 0 0 2i 0 3 (I8) Since the 180xC pulse and the delay 1 are suppressed.12). The density matrix just before the 90xCH pulse is then D (5) 2 0 0 3 B* 0 0 C* B 0 2 0 0 C 0 3 (I9) with B C 2i exp( i 2i exp( i 13 e t) t) (I10) 24 e We apply the 180xCH operator to (I9). D(5) R90 xCH 2 1 3i 2 2i 3 iB C B* iC * 2i 3 2 3i B iC iB * C* 2i 3 2 3i B iC iB * C* 2 iB 3i C 2i B * 3 iC * .51).Supplementary Discussions 177 2DHETCOR without the 180xC pulse We demonstrate here the result (I. taken from (I.
178 Appendix I Premultiplication with R 901xCH gives the following expression for D(7) 10 i (B B* C C*) 2i B B* C C* B C B* C* i( B B* C C *) 2i B* 1 4 B B C* C 10 i (B F* C i( B B* C C*) B C B* C* C*) (I11) C B* C* i( B B* C C *) 10 i( B B* C 2i B B* C C* C*) i( B C B C 2i B C 10 i ( B C B * C*) B* C* B* C* B * C *) We follow now the evolution of the carbon singlequantum coherences. Proceeding as in (I. This is why 2 still is necessary. If we start the acquisition at t(7).36) to (I.43) we have: d12 (8) d34 (8) d12 (7) exp( i id12 (7) exp( i C C 2 ) exp( i J 2 2 ) (I13) ) ) id34 (7) exp( i C 2 . 1 d12 (7) ( 2i B C B * C*) 4 d 34 (7) 1 4 ( 2i B C B * C*) d12 (7) d 34 (7) i (I12) The terms B and C. which contain the proton information. are absent from the sum. with the decoupler on. we will not have a 2D.
Supplementary Discussions
179
Treating the detection as in (I.44) to (I.47) we obtain
d12 (9) d34 (9)
id12 (7) exp( i id12 (7) exp( i
* M oC d12 9
C C
2 2
) exp( i ) exp( i
C d
t ) t )
(I14)
C d
M TC (9)
* d34 9 C 2
* iM oC d12 7
* d34 7 exp(i
) exp(i
C
C d
2
t )
)
t
(I15)
i ( M oC / 2)( B B * C C*) exp i
From (I10) we have
(td
t
B B*
2i cos
13 e
t
i sin
13 e
t
2i cos
13 e
i sin
13 e
C C*
M TC (9)
4i cos 4i cos
t 24 te
13 e 13 e
(I16) (I17)
i ( M oC / 2)( 4i cos 2 M oC (cos
13 e
t
4i cos t ) exp i
24 e C
t ) exp i (td
2
C
(td
2
)
t
cos
24 e
)
which confirms (I.51).
Fully coupled 2DHETCOR
If the proton decoupler is not turned on during the detection, the matrix elements d12 and d34 ,will evolve with different frequencies in the domain td. Each of them is proton modulated, even if their sum at time t(7) is not, and this renders the delay 2 unnecessary. The detection starts at t(7) and we will have
M TC (9)
* M oC d12 7 exp(i
12 d
* t ) d34 7 exp(i
34 d
t )
By introducing (I12), (I16), and (I17) in the expression above we obtain
M TC (9)
iM oC 1 2 cos iM oC 1 2 cos
13 e 13 e
t
cos cos
24 e 24 e
t exp(i
12 d
t )
t
t exp(i
34 d
t )
which confirms (I.52).
180
Appendix J
APPENDIX J: PRODUCT OPERATORS AND MAGNETIZATION COMPONENTS
Finding the magnetization components Suppose that at a given moment t(n) of the sequence we have the density matrix D(n) expressed in terms of product operators. The x magnetization components for nuclei A, M, X (we take a threespin system as an example) are given by:
M xA (n) M xM (n) M xX (n)
( M oA / p ' A ) coefficient of [x11] in D (n) ( M oM / p 'M ) ( M oX / p ' X ) " " [1x1] " D(n) [11x] " D(n)
(J1)
with similar expressions for My and Mz. MoA, MoM, MoX are the equilibrium magnetizations for the respective nuclei. The factor p' is related to the Boltzmann factor and has the expression
p 'A
pA / 2 N
A
/ 2 NkT
(J2)
with similar expressions for p 'M , p ' X (for two nuclei we adopt p, q instead of pA, pX ). N = total number of quantum states in the system (degenerate or not). For m nuclei with I = 1/2 we have N = 2m. The quantity 1/N represents the average population per state as the total population is normalized to l. The above procedure is justified by the relation (B17), keeping in mind the orthogonality of product operators (relation D1). Fast and slow magnetization components In the first part of this book, when deriving the magnetization components from the density matrix elements, we found it instructive to calculate separately the fast and slow components of the transverse magnetization (see Section I.3.9). This can be achieved in the PO formalism as well.
Product Operators and Magnetization Components
181
For an AX system (two spin 1/2 nuclei), one can split the MxA magnetization into Mx12 (fast) and Mx34 (slow) as follows:
M x12
M oA coeff. of [x1]+coeff. of [xz ] 2p' M oA coeff. of [ x1] coeff. of [xz ] 2p'
M x 34
with similar relations for My. For nucleus X the fast and slow components are:
M x13
M oA coeff. of [1x]+coeff. of [zx ] 2p' M oA coeff. of [1x] coeff. of [zx] 2p'
[1x] [ zx] 2
M x 24
Using Table II.1, one can check that [1x] [ zx] 2 and
represent the matrix elements d13 and d24, respectively. Writing the initial density matrix We assume usually that, before the pulse sequence starts, all spins are at thermal equilibrium with the lattice. With the sign convention adopted in this book (vide infra) the density matrix D(0) will be:
D (0)
This is consistent with
p ' A [ z11] p 'M [1z1] p ' X [11z ]
(J3)
M zA
M oA
;
M xA
0
;
M yA
0
and is the same for spins M and X. If we work in a steady state in which one of the nuclei (let's say nucleus A) does not have enough time to recover from the previous cycle, we can start with
D(0)
p ' A [ z11] p 'M [1z1] p ' X [11z ]
(J4)
182
Appendix J
1 . If MzA has been brought to zero by the last pulse of the where sequence and the start of the next sequence comes after a delay d, then
1 exp d / T1 A
Generally we start a sequence with no transverse magnetization; this implies that d is long enough with respect to T2 for all nuclei. Sign convention Throughout this book the conventional positive sense (right hand rule) has been adopted for all rotations (due to pulses or evolutions). For instance a rotation about Oz brings the magnetization from x to y, to x, to y. A rotation about Ox goes: y to z to y to z This is the actual sense of precession when the magnetogyric ratio, is negative. It has been assumed that the main magnetic field Bo is directed upwards (along +Oz) and thus at equilibrium the magnetization is directed up and the angular momentum is directed downwards (along Oz) which is also consistent with a negative . This way, the most populated state is the one with the angular momentum negative. Most features of the NMR sequences (one and twodimensional) do not depend on the sign of for all practical purposes. Commercial NMR spectrometers do not provide specific means to distinguish the sign of . Therefore the above rules can be applied for all nuclei in the system, no matter what the sign of their magnetogyric ratio. If for special purposes the sign of has to be taken into account, then for positive we have to use left hand rotation rules and start at thermal equilibrium with Iz directed upwards.
So. A coupled evolution can interchange x and y but also 1 and z. .When to Drop NonObservable Terms 183 APPENDIX K: WHEN TO DROP NONOBSERVABLE TERMS (NOT) In the expression of the density matrix we are interested in those POs which represent observable magnetization components: Mx and My for the nucleus (or nuclei) which are observed (see Appendix J). or just include them in the nondescript designation NOT. [1z]. An experienced student will find for example that if the observable is A and the last pulse is on X. We have to carry all the nonobservable terms through the calculations as long as there is a possibility for them to generate observable terms (following a pulse or an evolution). For instance. If a pulse still follows. it is recommended to use utmost care in dropping terms. we can do the selection earlier. [yzz]. terms like [1x]. (no x or y in position A) can be labeled as NOT before the pulse since an X pulse will never render them observable. [yz1]. [xz1]. even if coupled. Rule #2. if we observe nucleus A (in an AMX system). This includes the POs which show x or y for the observed nucleus and 1 for all others. [xzz]. Rule #1. Note. It is useful to be aware when it is safe to drop the nonobservable terms. [y1z]. [zx]. [y11]. [x1z]. Rule #3. Everything else is a NOT. In the final expression D(n) of the density matrix we have to write down explicitly the observable terms only for the specific nucleus which is observed. we can do some term dropping before the last evolution. In writing D(n 1) we will retain only the POs which contain x or y for the nucleus to be observed and z or 1 for the other nuclei. Although. if the last event of the sequence (the detection) is a decoupled evolution. when writing D(n 1). the following terms must be kept: [x11]. A decoupled evolution does not generate observable POs out of NOT or the reverse: it merely replaces x by y or y by x.
We make the convention that: {1z} = [1z11] + [11z1] + [111z] {1z} = [1z1] + [11z] {1z} = [1z] for CH3 for CH2 for CH Other examples of the { } notation: {1x} = [1x1] + [11x] {zy} = [zy11] + [z1y1] + [z11y] for CH2 for CH3 The sum { } has always n terms where n is the number of magnetically equivalent nuclei.184 Appendix L APPENDIX L: MAGNETIC EQUIVALENCE. we introduce here an even more compact notation (we call it the the multiplet formalism) to simplify the PO treatment of CHn systems. THE MULTIPLET FORMALISM While the PO formalism is basically a shorthand notation for density matrix calculations. In order to be consistent we have to write {z1} as: {z1} = [z111] + [z111] + [z111] = 3[z111] for CH3 {z1} = 2[z11] {z1} = [z1] for CH2 for CH . The density matrix at thermal equilibrium for a CH3 system is: D(0) = p'[z111] q'([1z11] + [11z1] + [111z]) (L1) We introduce the notation {1z} for the sum in parentheses and write D(0) as: D(0) = p'[z111] q'{1z} (L2) The notation {1z} is not only shorter but it allows us to write the last sum without specifying the number of protons in the system CHn. In such a system n nuclei out of n+1 are magnetically equivalent.
The above example may inspire us to hope that any sequence involving a CH2 or CH3 system may be treated as a CH. y or z. For instance [1xz] is not a legitimate term of such a sum. pulses do not break the { } formalism and can be treated according to the vectorial model.The Multiplet Formalism 185 With this convention we can rewrite (L2) as: D (0) ( p '/ n){z1} q '{1z} (L3) an expression valid for any n.f. Unfortunately this is not always true. No more than one of the protons may come in the PO with x. noncoupled evolutions (which are merely zrotations) can be treated according to the vectorial representation. Let us apply a 90xX pulse to D(0). We have done this in (L4). Rule #3 Likewise. Example: {zx} shift X {zx}cos X t {zy}sin X t We can satisfy ourselves that this is true in the case of CH2: shift X {zx} [ zx1] [ z1x] [ zx1]cos X t [ zy1]sin X t [ z1x]cos {zx}cos X t {zy}sin X t X t [ z1y ]sin X . the others must participate with a 1. Rule #2 Rotations due to r. D(0) 90 xX ( p '/ n){z1} q '{1 y} (L4) The expression above is easily obtained through the conventional PO rules applied to the expression (L1) or its equivalents for CH2 or CH. Rule #1 Not all the POs in the basis set can be included in { } sums. just by replacing [ ] with { }. It is important for the user of this formalism to be aware of how far the { } notations can be used and when we have to give up and go back to the explicit [ ] notation.
{zy}. {1y}.186 Appendix L Rule #4 A coupled evolution usually breaks the { } formalism. {zx}. A fortunate exception we can take advantage of is presented by the sums: {1x}. separately. {yz} or {xy} and a coupled evolution follows. The coupled evolution of any of these sums does not break the { } formalism and can be treated according to Section II. C cC n {x1} sC n { y1} NOT sC n {x1} cC n { y1} NOT sSC n 1{x1} cSC n 1{ y1} NOT cSC n 1{x1} cSC n 1{ y1} NOT NOT NOT NOT NOT C cos Jt . 2. Even here there is an exception and it is worth talking about because it may save a lot of term writing. NOT nonobservable terms s sin t . n number of protons S sin Jt . and 3. we have to give up the { } shorthand and go back to the regular PO formalism ([ ] notation). The above evolution rules can be verified by writing the product operators in the conventional way and calculating the evolution of the CHn system for n=1. Rule #5 If the density matrix contains sums as {x1}. In this case we are interested in the observable terms only (see Appendix K) and the coupled evolution yields unexpectedly simple results (we observe nucleus A): c {x1} { y1} {xz} { yz} {xx} { yx} {xy} { yy} cos C t . . The exception works when the coupled evolution we are talking about is the last act of the sequence or is just followed by a decoupled evolution.7. since it generates PO's that cannot be included in { } sums.
MoH is the equilibrium magnetization due to all n magnetically equivalent protons.The Multiplet Formalism 187 Rule #6 The procedure for retrieving the magnetization components in the { } formalism differs only slightly from that stated in Appendix J. . M xC M xH nM oC / p ' M oH / q ' coefficient of {x1} coefficient of {1x} (L5) with similar expressions for My and Mz.
Rotation axis in spherical coordinates. the angle value is defined by tan = B1/ . In Section II. For a deviation = Bo is different from 90o.1. pulses follow in the PO formalism the pattern of vector kinematics.f.f. The angle is the transmitter phase which is always taken with respect to an initially established receiver phase.1.1. its tr from resonance. In order to treat the general case (rotation axis with any spatial orientation) we use spherical coordinates as shown in Figure M. If the r. = 90o. The result of a rotation by an angle (right hand rule) about the axis defined above is described in Table M. pulse is applied on resonance.188 Appendix M APPENDIX M: ROTATIONS ABOUT NONTRIVIAL AXES Rotations due to r. z rotation axis y B1 x Figure M.6 we have discussed rotations about the axes Ox and Oy. The rotation axis makes an angle with Oz ( 0 180o ) and its horizontal projection makes the angle with Ox (positive sense for is from Ox toward Oy). .
Rotations about Nontrivial Axes 189 Table M. Initial component F i n a l c o m p o n e n t s I (1 cos ) x I (1 cos ) y I (1 cos ) z Ix sin 2 x cos 2 sin 2 y cos sin I cos I sin cos sin cos cos I sin z sin sin I (1 cos ) x I (1 cos ) y I (1 cos ) z Iy sin 2 cos sin sin 2 y sin 2 sin cos sin I sin z I cos I sin x cos sin cos I (1 cos ) Iz x I (1 cos ) y I (1 cos ) z sin cos cos I sin x sin cos sin I sin y cos z 2 sin sin sin cos I cos . Final Angular Momentum Components after Rotation by an Angle about the Rotation Axis Defined by Angles and .1.
Final Angular Momentum Components after Rotation by an Angle about an Axis in the xy Plane ( =90o) Defined by Angle .2 we consider the particular case of an onresonance pulse ( = 90o).2.190 Appendix M In Table M. Table M. Initial component F i n a l c o m p o n e n t s I cos x 2 2 I (1 cos ) y I sin z sin Ix I cos sin x cos sin I (1 cos ) x I sin y y 2 I sin 2 Iy z cos cos sin I cos cos Iz I sin x sin I sin y cos I cos z .
Initial component F i n a l c o m p o n e n t s I cos x 2 2 I sin Ix I cos sin x 0 z sin I sin y 2 I sin 2 Iy 0 z cos I cos cos y Iz I sin x sin I sin y cos I cos z Making equal to 0o. It is instructive to compare these results with those obtained by means of the vector representation. . 90o. as shown in Table M. 270o. 270o. In this case. Oy (phase cycling). in Table M. 180o. Final Angular Momentum Components after Rotation by an Angle about an Axis in the xy Plane ( =90o) with the Angle a Multiple of 90o.Rotations about Nontrivial Axes 191 Very often the phase angle can only take one of the "cardinal" values 0o. the product sin cos vanishes and the expressions above become even simpler.3. Oy. Table M. 90o. Ox. yields the rotation rules about Ox. 180o.3.3.
Madison. Principles of Magnetic Resonance. Longman Scientific and Technical Publishing Co.).E. Reidel Publishing Co. Ernst. 1988. 1987. G. T. D. Reidel Publishing Co. 1984.. Principles of Nuclear Magnetic Resonance in One and Two Dimensions. Berlin/Heidelberg/New York. O. G. 1984. VCH Publishers. Slichter. Sörensen. 501524.). Camille Sandorfy and Theophile Theophanides (Eds. TwoDimensional Nuclear Mgnetic Resonance in Liquids.Bodenhausen and A.R. Leonidas Petrakis and Jacques Fraissard (Eds. 213256. G." in Spectroscopy of Biological Molecules. 1988. P.R. "Teaching the New NMR: A ComputerAided Introduction to the Density Matrix Treatment of DoubleQuantum Spectrometry. 16.192 Suggested Readings Suggested Readings R. M. M. 1980. Ray Freeman. "Teaching the New NMR: A ComputerAided Introduction to the Density Matrix Formalism of Multipulse Sequences. Density Matrix Theory and Its Applications in Spectroscopy." in Magnetic Resonance. Mateescu and A.. Clarendon Press.. Dordrecht/Boston/Lancaster. Ernst. 1988. Weinheim/New York. Goldman. G. Quantum Description of High Resolution NMR in Liquids. .W. Ad Bax. Farragut Press. Clarendon Press. G. Wokaun.C.E.S. 163192. G. Dordrecht/Boston/Lancaster. Bodenhausen and R. WI. Progress in NMR Spectroscopy. Dordrecht/Boston/Lancaster. Oxford. Mateescu and A. 1991. Oxford. A Handbook of Nuclear Magnetic Resonance. Valeriu. Harriman. Reidel Publishing Co. D. Farrar and J. Valeriu.. Martin and A. TwoDimensional NMR Methods for Establishing Molecular Connectivity: A Chemist's Guide to Experiment Selection. SpringerVerlag. 1983. C. 1982. Eich. Zektzer. Performance and Interpretation. Essex. Levitt.
33 Enhancement factor. 152. 121. 23 doublequantum. 32. 127. 172 Complex conjugate. 42. 6066. 18. 76 Commutativity. 80. 67. 8. 5. 7678 constant. 164167 decoupled. 130. 20 F Fast scanning. 19 homonuclear. 137142 Angular frequency. 86. 105 Conjugation. 130 Eigenfunctions. 148. 14. 11. 146 D Decoupling. 58 Ensemble. 31 Density matrix. 60. 14. 31. 74. 1. 7. 41. 23. 135 Building block. 120. 105 real. 92 E C Chemical shift. 11. 168 Boltzmann. 76 Effective magnetic field. 7476. 57 Determinant. 102104 Acquisition. 163167 long range. 125. 180 distribution. 120136 Axis: imaginary. 37. 75. 60. 42. 105107 Avram. 4559 Coupling. 128. 116 definition. 3. 16. 36. 121. 68 Evolution. 121. 8283 shift. 20. 6067. 2. 49. 153158 Basis set. 77. 23.Index 193 INDEX A Angular momentum. 69. 59. 124. 127129 coupled. 5. 104 Argument. 112 Commutation rules. 43. 89 zeroquantum. 50. 51. 59. 35. 134 multiplequantum. 105 rotation. 44. 3. 159. 75. 98 Coherence. 83. 18. 11. 8. 36. 9. 17. 39. 17. 2. 73. 13 B BASIC. 76 singlequantum. 49. 4. 163 Cyclops. 81. 9. 17. 43. 121 Energy levels. 38. 94101 Detection. 36. 6567. 46 APT. 49 Doublet. 188191 intuitive picture. 20 weak. 87. 114 Domain. 11. 65. 104 quadrature. 43. 38. 89. 5. 60. 32 Bra. 3536. 163 Correlation: heteronuclear. 90. 147. 4. 116. 67 DEPT. 2. 45 COSY. 69. 120. 57. 39. 169170 coupling. 44 Contour plot. 65 evolution. 18. 57. 4. 57. 41 Eigenstates. 37 Connectivity: carboncarbon. 2. 123 Ernst. 9. 26. 19. 123 formalism. 1. 95 . 18.
127 observable. 136 elements. 125 HETCOR. 35. 58 Matrix. 133. 8386 transverse. 21. 48. 44. 93 formalism. 184187 L Label. 116. 41 Overlap. 123126 components. 105. 6. 18. 69 DM treatment. 110 adjoint. 25. 41 longitudinal. 81 Magnitude calculation. 58 N Nenitzescu.194 Index Frame: laboratory. 56. 174179 PO tratment. 25 INADEQUATE. 61. 8. 180 O Observable. 23. 20. 18. 2. 22. 8083 of CH 2 and CH 3 . 3144. 55 nondiagonal. 22. 88 Operators: evolution. 88. 106 Multiplet. 26. 57 Modulus. 59. 121. 59. 48. 11. 2. 129 Fourier transform. 125 inversion. 15. 20 Nonobservable terms (NOT). 182 H Hamiltonian. 44. 23. 11. 14. 85 180182 equilibrium. 63 63 I Imaginary unit. 38 fast/slow. 147 unit. 120. 90. 4. 161 Magnetization. 101 illresolved. 15. 9. 6. 129 Hardware. 5. 16. 25. 162 Hermitian matrix. 16. 83. 105 Imbalance. 23. 7. 120 Magnetic qantum number. 38 Larmor frequency. 74 change. 6 rotation. 127 Hermitian. 33. 49. 29 amplitude. 70 Modulation. 137146. 8793. 97. 10. 116. 11. 139 diagonal. 3. 59. 23. 49 phase. 121 premultiplication. 95. 116. 14. 116. 16. 58 . 41 observable. 145 INEPT. 1. 81. 110111 postmultiplication. 62 Normalization. 109116 derivative. 126. 183 M Magnetic moment. 8. 59 G Gyromagnetic ratio. 48. 122 addition. 3. 11. 24. 25. 8. 94 K Ket. 430. 34. 112114 multiplication. 17. 8. 129 rotating. 19. 1. 69. 116 algebra. 17. 63 trace.
82. 1. 93 V Vector representation. 42. 32. 35. 147 Transition frequency. 57 offdiagonal. 95. 48. 126. 18. 62. 7 equilibrium. 7. 134 Stack plot. 31. 100 Refocusing. 133 Shift: chemical. 99. 76 W Wave function. 64. 57 Quartet. 104 Rule(s): commutation. 127 difference. 124. 121. 69 Shortcut. 42. 94. 38. 87. 159162. 2130. 31. 88 Relaxation. 163 coupling evolution.1. 6079 treatment. 89. 59. 10 Product operator (PO). 45. 102 multiplet formalism. 64. 57 Phase cycling. 95. 129134 nonselective. 11. 73 sequence. 120123 . 33. 24. 182. 161. 32. 34. 126 Q Quadrature detection. 37. 171173 routine. 32. 127 Sequence. 99. 80104 Pulse. 20 T Thermal equilibrium. 1. 51 frequency. 5. 114 Sign convention . 71. 40. 2. 4. 94. 5. 32. 102 Series expansion. 171 shift evolution. 44 Transposition. 188 Recycle time. 74 S Satellites. 45 inversion. 35 Transmitter. 131. 106. 4. 108. 112. 5. 53. 57 diagonal. 87. 163 Shorthand. 45. 88 Right hand rule. 51. 9. 8. 65. 7073. 84. 52. 185187 nonobservable term. 62. 7.Index 195 P Peak: axial. 183 refocussing routine. 39. 61. 116 Triplet. 107. 102. 31. 182 Slichter. 7779. 159 coupled evolution. 4. 87. 7780. 191 Polarization transfer. 31. 52. 94 Population. 98 evolution. 92. 80. 53. 18. 64. 144146. 180182 definition. 84. 3. 5. 38. 94 Repetition rate. 109. 7074. 77. 18. 34. 88. 17. 147152. 93 R Receiver phase. 23. 13. 40. 59. 57 neardiagonal. 5159. 120. 188 Rotation. 15. 44 cross.87. 85. 92. 9. 188191 Trace. 31 Schrödinger. 6769 formalism.
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