Pulsed Spin Locking in Pure Nuclear Quadrupole Resonance: Additional Information On J. Chem. Phys

Pulsed spin locking in pure nuclear quadrupole resonance
R. S. Cantor and J. S. Waugh

Citation: J. Chem. Phys. 73, 1054 (1980); doi: 10.1063/1.440277
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Pulsed spin locking in pure nuclear quadrupole
resonancea) b)
R. S. Cantor c) and J. S. Waugh
Department of Chemistry. Massachusetts Institute of Technology. Cambridge. Massachusetts 02139
(Received 9 July 1979; accepted 9 October 1979)
The technique of pulsed spin locking in NMR has recently been applied to a pure NQR system, with
results very similar to those obtained in the NMR case. However, the theoretical methods used to explain
the NMR results are not applicable to the pure NQR case. Using a model of the NQR system, a method
is developed for following its evolution, which leads to results which reproduce the experimentally
observed short-time behavior. and which are in some agreement with the long-time behavior.
I. INTRODUCTION
To obtain high resolution NMR spectra in polycrystal-
line SOlids, various experimental techniques have been
developed, many of which utilize pulsed rf fields. In
general, these experiments have been performed in high
static magnetic fields, on systems of spins having rela-
tively little or no quadrupolar interaction. One of the
first such experiments, pulsed spin locking, developed
by Ostroff and Waugh! (OW), has recently been applied
by Marino and Klainer
2
(MK), to a significantly different
kind of system. MK studied a pure nuclear quadrupole
system, consisting of spin-l nuclei in a powdered solid,
having large quadrupolar interactions, in zero external
dc field, using the same type of pulsed (spin-locking) rf
fields as those used by OW in their NMR experiment.
. Although these are two very different systems, the re-
sults of MK were remarkably similar to those of OW.
Various theoretical methods have been used, with at
least qualitative success, to explain the results in the
OW NMR experiments. In an attempt to explain the time
dependence of the observed magnetization, average
Hamiltonian theory3 was used, 4 agreeing well with ex-
periment only for short time periods. Various approxi;..
mation methods were employed
5
to account for the long-
time behavior (decay of magnetization) with qualitative
success. Unfortunately, neither average Hamiltonian
theory nor any of the approximation methods is appli-
cable to the NQR case, for reasons which will be dis-
cussed. A different approximation technique from that
used to describe the NMR experimental results will be
developed here, and applied to a model of the system,
to account, qualitatively, for the effective spin locking
observed in the pulsed NQR experiments of MK (i. e. ,
the short-time behavior). The results will also help
somewhat to understand the long-time behavior, i. e.,
the dependence of the magnetization decay time on the
parameters which characterize the pulse sequence.
In the OW experiment, the spins in high dc field are
irradiated on resonance with the following pulse se-
quence. After an initial 90
0
(preparatory) pulse Po, the
sequence (T-P-T) is repeated many times, and the sys-
tem magnetization is sampled at the end of each repeti-
tion. By T we signify zero rf intensity for a time T; by
a) Supported in part by the National Science Foundation.
~ Submitted (in more extended form) by R. S. Cantor in partial
fulfillment of the requirements for the Ph. D. degree.
clpresent address: College de France, Physique de La Matiere
Condensee, 75231 Paris Cedex 05, France.
P we Signify a 90
0
pulse, phase shifted by h relative to
Po, as observed in the interaction representation in
which the dominant (Zeeman) interaction has been trans-
formed out of the total Hamiltonian (i. e., the coordinate
frame rotating at the Larmor frequency around the dc
field direction). Now consider the NQR case: a poly-
crystalline sample containing spin-l nuclei in zero dc
field subjected to the same rf pulse sequence. The sys-
tem is irradiated on only One of the three quadrupole
resonances. Now it will be shown that if we go into the
interaction representation in which the main (now quad-
rupole) part of the Hamiltonian has been transformed
out, then the effective pulse angle will not be 90
0
for
each spin, but will vary from one crystallite to another
depending on the relative orientations of the quadrupolar
and rf principal axis systems (QPAS and RFPAS). Thus
the Hamiltonian is not cyclic, and average Hamiltonian
theory therefore is not applicable to the NQR case. 3 In
addition, the approximation methods used to describe
the long-time behavior of the system in the NMR case
rely on the pulses being of equal intensity (of angle 90
0
)
for spins in all crystallites
5
; thus those methods cannot
be used in the NQR case either. That MK should obtain
the same results as those of OW is therefore not at all
obvious.
II. MODEL OF THE SYSTEM
We use the following model to discuss the NQR ex-
periment. The system to be studied is a polycrystalline
sample containing spin-l nuclei in zero dc magnetic
field. It will be assumed that the only contributions to
the spin Hamiltonian are: the quadrupolar Hamiltonians
for each spin i ( J C ~ ) , the dipolar interactions between
these nuclei ( J C ~ ) , and the pulsed rf interaction with each
spin of the OW type ( J C ~ ) . Since we are discussing a
system of many spins coupled b'y dipolar interactions,
we cannot hope to follow the evolution of the system ex-
actly. We consider, as a crude model, instead, an en-
semble of isolated two-spin systems, each system ran-
domly oriented with respect to the lab (i. e., the rf
field), depending on the orientation of the crystallite in
which it is found. Admittedly, this is a very poor ap-
proximation, but, as will be seen, it is a remarkably
good method for obtaining qualitative information on
short-time behavior of the system, and also, to a lesser
extent, for understanding the eventual decay of magne-
tization.
It will also be assumed, for the sake of Simplicity,
1054 J. Chem. Phys. 73(3). 1 Aug. 1980 0021-9606/80/151054-10$01.00 1980 American I nstitute of Physics
R. S. Cantor and J. S. Waugh: Pure nuclear quadrupole resonance
1055
that the quadrupole principal axis systems (QP AS) for
each of the two spins have the same orientation with re-
spect to the lab. (This is true of the t4N spins within a
crystallite- in the sample used by MK: NaN0
2
at 77 K).
III. GENERAL DESCRIPTION OF THE METHOD
The time development of the model system will be
described by the evolution of a reduced density matrix
p. Since the system contains two coupled spin-l nuclei,
this density operator will be represented by a 9 x 9
Hermitian matrix, and thus will be, in general, a time
dependent linear combination of 81 operators, an un-
pleasant prospect.
The method to be used relies on a major simplifica-
tion resulting from the nature of this particular experi-
ment. When the proper interaction representation is
chosen, and a special notation is used, then the evolu-
tion of the system is describable by a (transformed) p
which is a linear combination of only six operators, with
time-varying coefficients. The bulk of the calculation
will be concerned with this reduction. If we represent
this transformed reduced density matrix p by a vector
in a six-dimensional space, the components of which
are the time dependent coefficients of the six operators
comprising p, then it will be shown that both the effect
of a pulse and the effect of JeD (during the time the rf is
off) appear as rotations in this six-dimensional space.
In fact, it can be simplified further, for if we break up
this space into a direct product of two spaces, each of
three dimensions, then each of the two types of evolu-
tions, pulse and JeD' is represented by independent
analogous rotations, one in each of the two spaces.
Having demonstrated this, the (T-p-T) evolution will be
evaluated in this vector representation of p, as a reduc-
tion from three successive rotations to one rotation
about some axis, of some precession angle, in each of
the two spaces. Then it will be Simple to determine the
effect of N such (T-P-T) sequences; the two axes remain
the same, and the two preceSSion angles are each multi-
plied by N. Now, of these six operators, only two of
. them, one from each set of three, can generate any
Thus the time dependence of the appro-
priate linear combination of these two operators will be
proportional to the magnetization resulting from this
two-spin system. Remembering that the sample con-
sists of many such systems of random angles of orienta-
tion, appropriate integrals can then be performed to ob-
tain the time dependence of the magnetization of the en-
tire polycrystalline sample.
The evolution of the model system will be followed in
the interaction representation defined by the unitary
operator R = exp(i Jeot) in the following way. For any
operator A, we define an operator AU) such that A(t)
=RAR'. We have, for the equation of motion of the re-
duced density matrix p (to be defined more precisely
later)
p(t) == i[p(t), Je(t) , (1)
with Je(t) =:JCQ +Je
rf
+Je
D
Then it is easily shown that
== i[p(t), feU) + iRtR] == i[p(t), fert(t) +ieD(t)] . (2)
To obtain :lC
rf
and :feD' we need to express R == exp(iJeQt)
explicitly, which we choose to do in the quadrupolar
principal axis system (QPAS). We will then obtain JeD
and Je
rf
in that frame, and will calculate fe
rf
and :lC
D
We
then calculate p(O) as well. In so doing, we will adopt
the fictitious spin notation used by Vega and Pines
6
and
Shattuck
7
discussed in Appendix A.
IV. HAMILTONIAN OF THE SYSTEM
The quadrupole Hamiltonian for each of the two spins
(call them a and i3) expressed in the system
defined by the QP AS of each spin, is
8
Jei
o
= _II (Ii + 1) + 1]1 i === a or {3 ,
(3)
Now, if we assume that the QPAS's of the two spins co-
incide, then the coordinate systems will coincide. Also
== wo; 1]'" == 1J1l= 1]. In fictitious spin notation
6
1
(see Appendix A), we obtain
Using the relation 1: a + I
y
a
+ I ... a = 0, we can express
in two other ways:
- iwQ{a(3 + WI ,
== + 1]) - WI .
In general, then
P==x,Y,z,
where

- (t(3 -1J)JwQ, - [t(1 +1J)]w
o
,
a (2) b 2
W .. = - 31) W
Q
' W
I
= 3Wo .
(4)
(5)
(6)
(7)
Note that w;, are the three pure quadrupole reso-
nance frequencies. Now in each of the three ways of ex-
pressing the two terms commute; = O.
Thus, we can factor R as a product of four terms:
R =exp(iJeQt) = exp[i(w:I:.3 + W!I:.4 + w;I:.3 + W;I!.4)t]
= exp(iw;tl:.
a
) exp(iw!tl:,4) exp(iw;tJ:.
3
) exp(iw!tl:.
4
). (8)
(This will be useful in calculating JC...f and JeD')
We need to express the angular momentum operators
in three different coordinate systems, corresponding to
the quadrupole, dipole, and lab (rf) principal axis sys-
tems. To avoid confusion we adopt the following nota-
tion:
coordinate system notation
QPAS
DPAS
rfPAS x", y", z";IxII) 1 )I'"
To calculate both XD(t) and fc..t(t), we will need to know
how I!(p == x, y, or z) transforms going into the interac-
tion representation. That is, we must evaluate expres-
sions of the form
(9)
J. Chem. Phys . Vol. 73. No.3, 1 August 1980
1056
Now it was shown earlier that Je
Q
can be written in three
ways having the form = w; I!. 3 + w!.c;" 4' Note that I!

wt(t)=OM2:0[t-T(2k+1)] (all other pulses),
k=O
== 2I!.1 (going into fictitious spin notation). Remember-
ing that (see Appendix
A) and that the operators {I!.t,I!,2,I!,S} have the same
commutation relations as the three components of angu-
lar momentum V .. ,J"J
z
}, then we obtain
1!,t(t)=RIp,tRt=I!,ICOS(W;t) -I!,zsin(w;t) . (10)
Now, the relative orientation of I, .. and the QPAS de-
pends on the crystalline orientation, whiCh is random.
In general, we can represent this relation by two angles
(e L' (h) in the usual way (with y as the e=:o axis):
I! .. =: sine L sinLI! + cose + sine L . (12)
A. rf Hamiltonian
We irradiate on one of the three quadrupole reso-
nances; for example, as was done in the MK ex-
periment. Then
(lla)
(lIb)
Thus, in the QPAS frame, we get
= wt(t) + )(sine L sinLI! + cose
(13)
where
=: 0 (first pulse) ,
= h (all other pulses) .
.. (first pulse, t=O),
Je
rf
= - w
1
(t) (all other pulses) ,
where
Converting to fictitious spin notation and USing Eq. (10),
we c an now obtain :iC
rf
:
= 2w
t
(t) + )[sine L sinLU!, t -1;,z
i=a or f3; (14)
- - a -
:!C,.f = Jerf + Jert .
If we truncate in the usual way, i. e., ignoring terms which oscillate rapidly (or order w
Q
), we obtain
(first pulse) (15a)
= eM cose Lei;; o(t - T(2k + (all other pulses) . (15b)
B. Dipole Hamiltonian
Expressed in its own principal axis system, we have

(16)
where Tr.o is an irreducible tensor operator; we use the convention of Haeberlen.
8
Here, w
D
=: -2yZn,lf As-
suming, for generality, that the DPAS and QPAS are randomly oriented with respect to each other, then we can ex-
press JeD in the QPAS by using the appropriate Wigner matrix for that transformation. Again adopting the notation
and conventions of Haeberlen, 8 we have .
Z
2: :nt_mT z.m(-I)m
wD m=-Z
(17)
=,p; sinZe (T
D
e-
2i
I/! D + TD e+
2i
I/! D _ v'T sin20 (T
D
e-/I/! D _ TD e
i
I/! D) + 1.(3 cos
2
8 _1)TD
a D Z,Z Z,-2 8 D Z,1 2,-1 2 D Z,O
.ff . 2 2 ('" 8 .. 8) (3 cosze D -1) (2 a 8 a 8 .. 8)
= llsmeDCOs DI"Ix-I,I, + 2N IzIz-I"I,,-IyIy
+ ,If [ + sin
2
e + I;m + sin2e DcosD(I:I! + + sin2e D + .
(18)
Changing notation, as before, we obtain
JeD = 2w D[a" I:, 1 1:,1 + ayI;.l Ie.1 + a.I:, + bU:, + I;. 1 I!. 1) + cU:. 1 1 + , (19)
where
a,,=v'f sin
2
8Dcos2D -(1/,16)(3 COs
2
e
D
-1) , a
y
= - v'f sin
2
8Dcos2D - (1/,I6)(3cos
2
e D -1) ,
az=(2/v'6)(3cos
2
eD-1)
To calculate JCD(t), consider a bilinear operator of the general form 1:.11:.1; JeD is composed of a sum of nine such
terms. Now
J:.ti!.t(t) = exp{iJe
o
t)I:.
t
I:.
t
exp( - iJeot) . (20)
Using Eqs. (8) and (10), and remembering that we obtain
i:.
t
i:, t(t) = exp(iw;tI:. 3)1;, t exp( - iw;tI:.
3
) exp(iw:tI:, 3)1:, 1 exp( - w:tI:. 3)
= (1;,1 cos(w;t) -1;.2 sin(w:t) ][1:,1 cos(w:t) -1:,2 sin(w:t) 1 .
J. Chern. Phys., Vol. 73, No.3, 1 August 1980
(21)
1057
Now, unless p == q, this is purely oscillatory. If p == q,
then there i$ a nonzero static part, so we use the fol-
lowing truncation as an approximation:
(22)
Thus, in this approximation, the only terms in :ito to
survive are the first three in Eq. (19):
:it
D
== W D[ax(I:.l + a/I;. I 1 + 1;.2

We choose to regroup terms for reasons that will be-
come clear later:
where
L '"
1:==woTWa.+ax)],
(-1:,11=.1

+IY.2IY,2) '
V. TIME DEVELOPMENT OF THE SYSTEM
(23)
It has been shown that to good approximation, :iC
v
is
independent of time, and 3Crf depends on time only as
does the pulse envelope. Now when the rf is turned on,
:!CD +:fc", ",3C
rt
When it is off, :iC
o
+3Crf ==1e
D
Thus, dur-
ing the preparatory pulse we can easily integrate Eq.
(2), the equation of motion of p, to obtain
p(O) == exp( - i8
0
1 hl)P(t < 0) exp( + i8
0
Iy.l) ,
where
(JO===(JMOCOSOL, ly.l==I:. 1 .
(24)
We have set t == 0 as the time of the preparatory pulse.
In the same way, for the other pulses
(25)
where ,A denotes after pulse, <B denotes before pulse,
and where
(J == 0 MCOSO L, I y
2
+ .
During the time (c..t) when the rf is off, we can integrate
the equation of motion just as easily:
iXto + c..t) == exp( -3C
D
c..t)p(to) exp( + ilc
D
c..t)
Setting c..t==T, if we let D==exp(-i3C
D
T), Po
=exp(-i8
0
1
y
1
), and then we can solve
for p(2kT) by calculating
p(2k7-) = O)P1{DPD)U
= (DPD)"p(O)(DPD}tk (26)
We wrote :reD as a sum of three terms in Eq. (23).
But [L,M]== [L,N]== [M,N]=O (see Appendix B). Thus
we can write D=DLDMD
N
, or any permutation, where
DL=exp(-if:L),
(27)
This will be useful, because it will be seen that of these
three propagators, at least two will have no effect on
any given term in p(t)-at any time.
A. Effect of preparatory pulse
Before the preparatory pulse, the system is assumed
be at equilibrium under the influence of the Hamilto-
n!an JC =JC
Q
+JC
D
;:::JC
Q
Using the high temperature ap-
proximation, 9 we get
o( t < 0) "" {Tr[ exp( - JCQ/kT}-l exp( - JCQ/kT)
"" [Tr(I)-I(I-JC
Q
/kT) . (28)
The first term is unaffected by any evolution of the
system, so we need only follow the evolution of the sec-
ond term, proportional to the reduced density matrix p,
which we define by setting a=[Tr(1)-1[1_(1/kT)p).
Thus, p(t< 0) ==JC
Q
)CQ is invariant going into the inter-
action representation. Thus,
p(t<O)=3C
Q
=JC
Q
= L (29)
i =0:,13
[From this point on, unless specified otherwise, all cal-
culations will be done in the interaction representation,
so the tilde (-) notation will be dropped. )
To calculate p(O), we use the following properties of
exponential operators. For three operators A, B, C;
scalar k, if [A, B]=iC and [A, C]= -iB, then
e-
ikA
B e+
ikA
:= B cosk + C sink,
e-
i
kAC e+
i
kA := C cosk - B sink .
Also, of course, if [A, B]== 0, then e-ikAB e+
ikA
=B.
Thus, we calculate
p(O) == Pop(t< 0)P1
(30)
(31)
where we have chosen the form of p(t< 0) with p == y,
[Eq. (29) and where Iy,i =1;,1 ==/:.
1
1
6
+ 1 "'Ie. I (1'" is
the single-spin identity operator for spin <1; likewise
for (3).
We now define a few new operators:
i=1,2,3,
U1 i= 1,2,3 ,
WI == i(Yj + U
i
), i == 1, 2, 3 ,
Vj==}(Y
i
-2U
j
) , i==I,2,3
(so Yj == Wi + Vj)' Thus, in this new notation,
p(O) = cosO o(W
a
+ Va)
(32)
(33)
We choose these operators because they have the above-
mentioned properties of operators with respect to the
exponential operators D and P [see Eq. (30)], as we
shall see, so their time development can easily be ex-
pressed.
J. Chern. Phys . Vol. 73, No.3, 1 August 1980
1058
B. Evolution after preparatory pulse
To begin, we calculate Dp(O)Dt. We will need to know
certain commutation relations, the method of calculation
of which is outlined in Appendix B (as will be all the
commutator calculations henceforth):
[lC
D
W
a
]= [:TeD' Va]:::: [:Te
D
,I
y
,4]=0 ,
[L, W
2
]=[L, V
2
]=[M, W
2
]=[N, V
2
]=O.
Thus,
per) == Dp(O)D
t
== cosBo(W
a
+ V
3
) +
- sinBo(D
N
+
Consider the following commutation relations:
[N, W
2
J==iS
2
,
(34)
[M, V
2
]=::iR
2
, +1:,1[:,2 ;
also
[N, 52] == - iW
2
, [M, R
2
] =:: - iV
2
.
Thus, by Eq. (30),
DW
2
D
t
:::: DN = W
2
cos1J + 52 sin?] ,
DV
2
D
t
=D
M
.
(35)
Now we know the effect of D on two other operators as
well:
DS
2
D
t
=D
N
S
2
D1 =S2 COS?] - Wzsin?] ,
- .
Thus,
p( r) == cosBo(W
a
+ Va) + - sinBo(W
z
COS?]
(36)
+ S2 sin1J + V
z
+ R2 . (37)
We started with a density matrix at t= 0 which was a
linear combination of five operators: {W
a
Va, 1
Y
,4' W
z
,
V
z
}. After following its evolution under the influence of
:TeD for a time r, we find the first three unaffected, the
coefficients of the last two changed, and the addition of
two more operators, {S2' R
2
}, bringing the total number
of operators comprising p( r) to seven. Now we must
examine how each of these seven operators is affected
by a pulse, and how many new operators are generated.
Remembering that P:::: exp( - iBI y, 2) :::: exp{ - iB Y2), we need
to know the commutators of Y
2
with each of the seven
operators comprising per). Calculations reveal
[Y
2
, W
z
]= [Y
2
V
2
]= [Y
2
,1
y
,4]= 0,
[Y
2
,R
2
]==iM,
[Y
2
,S2J=::i2Q2,
[Y
2
, W
a
] == iW
I
,
[Y
z
, Va)==iVj
In addition, we calculate
[Y
2
,M]=-iR
2
, [Y
2
,Q2]==-i2S
2

[Y
2
Wd==-iW
a
, [Y
2
Vd=-iV
3

ThUS, by Eq. (30) we obtain the effect of a pulse on all
seven operators:
PWzp
t
= W
2
,
PV
2
p
t
= V
2
,
P1
Y
,4
Pt
=ly,4 ,
PR
2
P
t
= R2 cosB + M sinB ,
P5
2
P
t
=5
2
cos2B + Q
2
sin2B ,
PWapt:::: Wa cosB + W
t
sinB ,
PVapt = Va cosB + Vj sinB .
(38)
We also know now how P affects four other operators:
PMp
t
= M cosB - R2 sinB ,
PQ2
pt
= Q2 cos2B - 52 sin2B ,
pwjp
t
== Wj cosB - Wa sine,
PVjpt = Vj cosB - Va sinB .
(39)
We have added four more operators {Wj. Vj, Q2' M} to
bring the number of operators in our set to 11, a linear
combination of whic h constitutes p( r - P). We have also
determined how these four are affected by pulses. How-
ever, we now need to know how these additional four op-
erators are affected by the propagator D in order to cal-
culate p(r-P-r); we already know the effect of D on the
other seven.
We obtain the following commutation relations of the
four operators with the three (commuting) parts of :TeD'
{L,M,N}:
[L, wd=[M, Wj]=O,
[N, wd = - i5j , 5j = + ,
[L, Vj)=[N, Vj)=O,
[M, Vt1=-iRj ,
[L, Q2] = [M, Q2)= [N, Q2)= 0 ,
[L,M]=[M,M]==[N,M]=O.
Thus,
DW
1
D
t
=DN = WI cos1J - SI sin7) ,

DQ2
Dt
==Q2,
DMDt=M.
(40)
Also, we obtain the effect of D on two new operators:
DSjD
1
=D
N
S jD1=Sj cos7)+ Wjsin?] ,
DRjDt = D.vRjD1=R
l
+ VI .
(41)
We have added two new operators {Rt> SI} so the set now
contains 13. We know how all 13 are affected by the di-
pole evolution operator, and how all but these two are
affected by a pulse. To obtain these last two bits of in-
formation, we calculate
[Y
2
, st1 == iSs , +1:,2/ :,1) ,
[Y
2
,Rtl== 0 ,
[Y
2
,Ss):::: -iS
t

J. Chem. Phys., Vol. 73, No.3, 1 August 1980
l059
Thus
PStpt=StcoSB +S3 sine ,
PRtPt=R
t

(42)
Also, we have the effect of P on the new operator:
PSsPt=S3COse -Sjsine . (43)
Having generated one more operator {S 3} we need to
know how it is affected by the three evolution operators
comprising D. Calculations give
Thus,
DS
3
D
t
=S3
(44)
and no new operators are generated.
The set of 14 operators is now complete in the follow-
ing sense. If we start with a reduced density matrix
which is any linear combination of these 14 operators,
and allow it to evolve under an arbitrary sequence of the
propagators P and D, the result will always be some lin-
ear combination of these 14.
We can now group these operators into five sets as
follows:
{Iy,4}; {V
3
, V
1
, R
1
}; {W
3
, W
1
, S3, S1}; {W
2
, S2' Q2}; {V2' R
2
, M} .
A glance at the results of the preceding calculations re-
veals that with respect to the propagators P and D (con-
sider them as operations) acting on the 14 operators
(consider them as elements), these subsets are indepen-
dent. Thus, although p{O) is actually a linear combina-
tion of five of the 14 elements (each in a different sub-
set), we can treat the evolution of each separately, in
that an element of one of these five sets can never gen-
erate any amount of an element in any of the other four
sets.
In addition, since we can only measure magnetization
in an experiment, we would like to know only about those
terms in P which can result in magnetization. Calling
this subset of the 14 operators {m}, then if A is in {m},
Tr{AM y) * O. Now, the magnetization operator (at the
resonant frequency in phase with the pulses after the
first pulse) expressed in the (static) lab frame, is
My=I
y
.. (in units of yn). (45)
In the interaction representation,
M, = (- elJCot(sine L sin<pL1x + cose Lly + sinB L cos <PLI.) e-IJCo
t
= - 2 L - + cosB -
+ sine L cos<p - cose L1y, 2 (46)
(truncating the rapidly OSCillating terms). Thus, we
need to know which operators (A) of the 14 obey Tr{AI
y
,2)
*0.
Of the 14, only two have this property: W
2
and V
2

ThUS, we need follow the evolution only of that part of P
containing the two independent sets {W
2
, S2' Q2} and {V
2
,
R
2
, M}. Analyzing the previous calculations, we see that
these two sets of operators behave analogously with re-
spect to each of the "operations" P and D. This is sum-
Jllarized in Table I. If we replace W
2
by V
2
, S2 by R
2
,
Q2 by M, 1) and 2e bye, we see that the second set
behaves in the same way as the first.
To understand the effect of the entire pulse sequence
on that independent part of P which results in magnetiza-
tion, call it Pm, which is composed of these six opera-
tors, we develop a new representation for Pm' We rep-
resent Pm as two three-component vectors, each in its
own space. In one space the axes are represented by
the three operators {W
2
,S2,Q2}; in the other, by {V
2
,
R
2
, M}, in the following sense. If Pm = aW
2
+ bS
2
+ cQ
2
+ dV
2
+ eR2 + fM, where {a, .. ,j} are (time-dependent)
scalar coeffiCients, then the vectors are defined by the
coefficients: (a, b, c) and (d, e,f). Let
Pm! == aW2 + bS
2
+ CQ2' P
m
2 '" dV
2
+ eR
2
+ fM (47)
We examine just the first vector Pm!> since all that fol-
lows will be applicable to the second as well. Identify
W
2
with y, S2 with X, and Q2 with z. Then the dipole
evolution (D) appears as a rotation of angle (-1)) around
the Q
2
= z axis. A pulse (P) appears as a rotation of
angle (-2e) around the W
2
=y axis. Thus, the evolution
of Pmt corresponding to (T - P - T) can be viewed, in this
space, as a sequence of three rotations; first a rotation
of angle (-11) around Z, then (-29) about y, then (-1))
about z. But this is Simply the Euler-angle definition of
one rotation of coordinates about some axis in 3 -space
with a =1), (3=2e, 1'=1); (a, (3,y) are defined using the
Haeberlen
8
conventions. This three step process can
therefore be represented by defining the axis of the one
overall rotation, the initial vector [the representation of
Pmt(t= O)}, and the precession angle. We accomplish
this in the follOwing way, using Pauli algebra notation. to
If we let r be the vector form of Pmt, then we repre-
sent it by the operator R=r where
ax, ay, a. are the Pauli spin-i matrices. Now, we can
TABLE 1. Effect of propagators on Pm'
Component of P Effect of P Effect of D
{W2
W
2
W
2
cosT) + 52 sinT)
Pm! S2 52 cos20 + Q2 sin20 8
2
cosT) - W 2 sinT)
Q2 Q
2
cos20 - 8
2
sin20 Q2
r
2
V
2 V
2
+ R2
P.,,2
R2 cosO +M sinO R2 - V2
M cosO - R2 sinO M
1060
represent a rotation of angle rJ> of r about some axis it
as R' = URUt, where R' is the Pauli algebra representa-
tion of r' (the result of the rotation), and
U=u
o
l+u'a
== exp[(-1irJit a] ,
where
,
(48)
(49)
(50)
UN = (UI)N "" exp[ - 0 a] .
We would like to convert this to the form
UN=uN.ol +u
N
' a .
But. using Eqs. (50) and (55).
u
n
o
= cosONrJ = cos[N cos-
1
(cosO cosn)]
= cos(N cos-
1
Ut,o) ,
(56)
(57)
(58)
u = - i siniii = - i(t - .
For the dipolar evolution,
(51)
where we define UI,O,,"UO(T -P -T). Now, by Eq. (51),
UN == - i
uT=z, rJ>=T/; U
T
=exp[-i(n/2)u
z
]'
For the pulse,
uP=Y. rJ>=2e; Up=exp(-iBu).
Thus,
= - i sin(N COS-IUI,olu
=sin(Ncos-
1
Ul,O)Ul(1-ui,ot1l2,
where UI =U(T -P - T).
We define
(59)
U( T - P - T) = UTU pUT = [cos(n/2)1 - i sin(T//2)u.)
uN,y,,"sin(Ncos-1ul,O)(-isin8)(1-uLo)"I/Z, (60)
x [cosln - i sinOuy)[cos(n/2)1 - i sin(n/2)u.]
= cos8 cosT/I - i sin8uy - i cos8 sinnu z (52) Then
(62)
where we have used the relation upu
q
"" iENrU. and u; "" 1.
Thus we can represent the (T -P - T) sequence by
lto = cosB cosT/ , (53)
(54)
Now, Pmj(O)=aW
2
; Thus, R(t=O)=acJ
y

and therefore,
U = - i sinBy - i cosO sin17z
with u = i u(l -
We obtain the precession angle of the (T - P - T) se-
quence by examining uo. By Eqs. (50) and (53),
R(2NT) = UNR(O)U%
1rJ>=cos-
1
(cosBcosn). (55)
Thus, by Eq. (49),
Uj = U( T - P - T) = exp{l- rJ}u u} ,
USing the relation ,0 - ,y - " = I, we obtain
R(2NT) = a[(1 + 2u1,.)uy - 2iu
N
,oU
N
,/J
x
- 2u
N
,yUN,.U
Z
]' (63)
Returning to operator notation:
where irJ> and u are given above. Now the result of N
such sequences will be to multiply the angle by N,
C. System magnetization
Pml(2NT) = a[(l + 2u1,,)w
2
First we calculate (My,pml)' the magnetization due to Pml, using Eqs. (61), (64), (53), and (32):
(M
y
,p,)2NT = Tr[p",t(2NT)(cOS8 Lly,z)] = (cosO L)a(l + Tr(W
2
1
y
,Z)
2 2 2 2 2 -1 ( cos
2
0 sin
2
1/ )]
=acosBL(1+2uN.hTrly2=-3wysmOOcosliL 1-2sm[Ncos (coslicosn)] 1 2/1 2
, , -cos cos 11
(64)
(65)
Substituting in the preceding calculation Pm2(O) =dV
2
for Pml(O) =aW
2
, for n, and {V
Z
, R
z
, M} for {W
Z
, 52' Q} in Eq.
(64), we obtain the magnetization due to Pm2:
(M
y
,.,)2NT = Tr[PmZ(2NT)(cos8 L1".Z)] = (cose L)d(1 + ... ) Tr(V
2
I y,z)
z 1 2 1 a . r,. 2{ -I[ (1.) ]}( ),1
=dcosBL(1 + 2uN )(3
Tr1
y.2) = - 3WysmeOcoSliL e -2 sm Ncos cos 2
0
J '
since d = a = - sine. The total magnetization is
(M) = (MY'Pmt> + (MY,P
m
2)
We can easily calculate the initial magnetization
(My(O = Tr[Pm(O) cosB Ll,,2] = - sinO 0 cosO L Tr(W
2
+ V
2
)Iy
2
= - sin8
0
cos8 L ,
J. Chem. Phys., Vol. 73, No.3, 1 August 1980
(66)
(67)
where eO=eMoCOse
L
. Thus, using Eqs. (65)-(67),
(M
y
(2NT == (M y(0(1 - A) ,
with
. A'" Hsin
2
[N cos-
1
(cose COS17)] cos
2
e sin217(1 - cos
2
e COS217rl
+ t sin
2
{N [1 _ ]-1} ,
where e == eM cose L; eM is the integrated rf pulse intensity. Now, using Eqs. (19) and (23), we obtain
== (w DT)( + v'f)[(3 cos
2
e D - 1) - sin
2
e D COS2<PD], 17 == DT)( - 4)[M3 cos
2
e D - 1) + sin
2
e Dcos2<pD] .
1061
(68)
(69)
(70)
The dependence of the magnetization on the parameters characterizing JeD' {W D' eD' <PD}' is contained completely in
and 17. It is assumed that even for nearest neighbors (i. e., for largest W D) WDT 1. Thus, 17 1 and for all
possible choices of pairs of spins within each crystallite, and we can replace 17 and by average values Tj and t
which are of order (w D T). Also, e L depends upon crystallite orientation; it relates the lab and quadrupole PAS's.
Thus, to obtain the total magnetization due to all the spin pairs of a given (w
D
, eD' <PD) in the entire sample, we do an
ensemble average over e L;
(My(2NT == (My(O - A(My(O .
Therefore, using Eq. (68), the fractional loss in magnetization is
F'" <MTo -(My(2NT == A(My(O
(M)O (M/O
We can calculate (M/O easily, using Eq. (67),
(My(O == - sin(e MO cose L) cose L
Thus,
-- 1 j2< j8L=< w
a
(My(O == -4 d<pL sine L de L[(My(O] == i?-(e M cose M - sine MO)
7T 0 8 L =0 IJ MOO 0
(71)
(72)
(73)
We can determine e MO from this expression, because in the experiment, 2 the pulse intensity is chosen to maximize
(My(O; setting (d/ de Mo)(My(O == 0, we obtain the relation
tane
Mo
==2e
M
/(2 -e10) . (74)
eMo :::;2. 08 :::;119 is the smallest such e MO. It is not 90, as MK state. 2 This gives
(My(O == + - e M/(4 + et/12] "" - O. .
Now, since Tj and 1, we can approximate
sinTj""Tj,
and substituting into Eq. (69), we obtain
A "" Tj2 + t sin
2
( H2 ,
where e = eM cose L. Thus, using Eqs. (67) and (76),
A(My(O ==A Tj2 + BP ,
with
1 w
a
I8
M
(Ne) (8)
= - "3 it -8M de sin
2
2"" cot
2
2" (e sine) .
(75)
(76)
(77)
Now in the experiment of MK, eM = e MO ::::119. In that case, A and B, although they depend on N, are never of
greater magnitude than of order Thus, using Eqs. (70), (72), (75), and (77), the fractional loss of magnetiza-
tion is of order (WOT)2 1.
1062
VI. DISCUSSION
We have seen that this model predicts almost com-
plete refocusing of the magnetization, i. e., spin locking
when observed stroboscopically. Thus it reproduces the
short-time behavior observed experimentally. 2 The
long-time behavior (magnetization decay) is not pre-
dicted by this model. This is not surprising considering
that the decay depends intrinsically on the many-spin
nature of the real system, which, of course, the model
cannot handle, by its definition. However, we could ap-
ply to the model a technique similar to that used by
Waugh and Wang, 5 a kind of molecular-chaos approxi-
mation, which leads to the conclusion that the charac-
teristic decay time increases as the time between
pulses decreases, which is observed experimentally,
although the functional dependence of on T is not ob-
tained.
APPENDIX A: FICTITIOUS SPINY2 OPERATORS
Vega and Pines
6
and Shattuck? have developed a nota-
tion which is very useful for describing those spin-l
quadrupolar systems in which the quadrupolar Hamilto-
nian is dominant. We adopt this notation, with some
additions and modifications, summarized as follows:
Define, for each spin,
We will need to know various commutation and anti-
commutation relations among these operators, as fol-
lows:
commutators:
[I/>.I,lp,J]=ilp
k
, i,j, k cyclic,
[1/>.1,1/>.4]=0,
[I/>.I,I tl=tiI
r
1
\
[Ip.l,I 2]=-tiIr.2 , p,q,rcyclic,
[1/>.2,1 2]= -tiIr.l
[Ip.l,I 3]=tilp.2 l
[ ]
1 P *q ,
I p
2
,I
3
= -zilp
1
'
[I P. 3' 1 3] = 0 ,
[I
x
1
, I y
4
] = il
x
2
,
[Ix.2,I y
4
]= iIx.l ,
[Ie.t>I y
4
]= iI
z
2
,
[Iz.2,I y4]=%iI 1 ;
anticommutators:
[Ip.I,Ip.J]t=O, i*j,
[IP.l,I tl
t
=t
lr
2
!
[Ip.l,I 2]t=tlr.l ,
[Ip
2
,I
2
]t= -tlr.2
[Ip1,! 3P = tlp.lt
[Ip.2,I
3
)t = tIM)
, p, q cyclic,
[IY.i,Iy.4]t=Iy.i, i=I,2
[Ip.i,IY.4)t=-tlp.i, p*y, i=I,2.
Also, we note the following additional properties:
I x,3+
I
Y,3+ I z,3=0,
1;,1 =1;.2=1;,3= +I/>,4)' p=X, y, z
21;,1 +Ix,3=2I;,1 -Iz,3= t(1-2Iy ,4) .
APPENDIX B
We have defined the following operators:
L ,
M= ,
,
Y
i
= 1 + I;,i 1
8
Ui =I;.i
Wi = t(Y
i
+ Ui)
Vi = t(Y
i
-2U;)
, i = 1,2,3 ,
5
2
= ,
,
,
Rl=Ix",1
,
where
Je
D
= + +T/N)
First we need to show that L, M, and N mutually
commute, and then to determine the commutators of L,
M, N, and Y
2
with each of the 14 operators compriSing
p. Since these operators are sums of bilinear opera-
tors, the commutators will be broken down into sums of
commutators of bilinear operators. We need then to
calculate commutators of the form [A" B
8
, C" DB], where
A, B, C, D are Single fictitious spin-t operators. Now
[A" B
8
, C"DB] = t([A", C"][BB, DB]t + [A", C"]t[BB, D
8
]) ,
so we only the single spin commutation and anti-
commutation relations, which are listed in Appendix A,
in order to calculate the bilinear commutators. The
calculations are quite lengthy, and are performed else-
where.
11
We summarize the results by listing only the
nonzero commutators of L, M, N, and Y
2
with the 14
operators comprising p:
[M, vtl = - iR(, [Y
2
, wtl = - iW
3
,
[M, V
2
]=iR
2
, [Y
2
, W
3
]=iW
l
,
[M,R
2
]= -iV
2
, [Y
2
, V
1
]= - iV3 ,
[Y
2
, V
3
]=iV
l
,
[Y
2
,5
2
]=i2Q2,
R. S. Cantor and J. S. Waugh: Pure nuclear quadrupole resonance 1063
[N, wtl=-iS
t
, [Y2,R
2
]=iM,
[N, W
2
]=iS
2
, [Y
2
, M]= -iR2
[N, S2] = - iW
2
, [Y
2
Q2] = - i2S
2

[N,Stl=iW
t
, [Y
2
,Stl=iS
3

[Y
2
,S3]=-iS
t
IE. D. Ostroff and J. S. Waugh, Phys. Rev. Lett. 16, 1097
(1966).
2R. A. Marino and S. M. Klainer, J. Chern. Phys. 67, 3388
(1977).
3U. Haeberlen and J. S. Waugh, Phys. Rev. 175, 453 (1968).
4J. S. Waugh and C. H. Wang, L. M. Huber, and R. L. VoId,
J. Chern. Phys. 48, 662 (1968).
5J. S. Waugh and C. H. Wang, Phys. Rev. 162, 209 (1967).
6S. Vega and A. Pines, J. Chern. Phys. 66, 5624 (1977).
7T. W. Shattuck, Ph. D. thesis (Univ. California, Berkeley,
LBL-5458, 1976) (unpublished).
BU. Haeberlen, High Resolution NMR in Solids (Academic, New
York, 1976).
sM. Goldman, Spin Temperature and Nuclear Magnetic Reso-
nance in Solids (Oxford U. P., Oxford, 1970).
IOL. Tisza, "Applied Geometric Algebra," Course Notes for
Physics 8.352, M.LT., 1976) (unpublished).
II R. S. Cantor, Ph. D. thesis (M. LT., 1979) (unpublished).

Pulsed Spin Locking in Pure Nuclear Quadrupole Resonance: Additional Information On J. Chem. Phys

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Pulsed spin locking in pure nuclear quadrupole resonance

R. S. Cantor and J. S. Waugh

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