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of cross relaxation

V. E. Zobov and V. N. Provotorov


tn*trute of chemical Phpics, Academy of sciences of the ussR, Moscow (Submltted November 1, 19?4) Fiz. Tverd. Tela, 1?, 1298-1304 (May 19?5)
The probability of two-spin cross relaxation is calculated with allowance for gradual rransfer of energy from dre two. flipPed spins to the remaining spins of the system. The rare of loss of energy by the paii, vhich depends on the way in which the field of the external spins varies. is esdmated io the framework of *te random-field method for discontinuous and continuous variations of rhis field. It is found that in rhe latter case the flow of energy from the pair to the other spins of rhe sysrem is slower.

of solids an importatt role is played by cross-relaxation processes, rhtch were first considered in ref. 1. In that paper the probability of cross-relaxation processes was calculated 11 accordance with the known expression of perturbation tbeory for systems with a continuous energy spectrum. h

tbe physics of the magnetic resonance

for the simplest two-spin cross-relaxation transition, in sNch two spins i and j of different species with resonance frequencies @ro and c,r2s are simultaneously flipped into the opposite direction (flip-flop process), this expression is
urj -h-2 lV;i
It g

nonresonance spins. Moreover, in some cases such nonresonance cross-relaxation processes cen play_a decisive role. To investigate the nonresonance mechanism, it is necessary to sfudy in detail the energy exchange between

characterizes the dipole-dipole interaction between spins responsible for the cross-relanation processes. However, this assumption is not necessary. In reality, tle crossrela:<ation process can also occur quite strongly between

magnetic moments, rnd'c is their concentration), which

(*1:),

(1)

a pair of spins that participate direcily in the cross re_ laxation and the remaining spins of the system.

*here Vi3 is the matrix element of the transition; g(ro) is the level density of the continuous spectrum in the final Etete, a form ftmction that reflects the ability of the spin system to tiberate or take up the energ'y firl, = h(arrooro)'

We now turn to a detailed treatment of t}e nonreso_ nance mechanism. We shall first consider the example of magnetically diluJe systems with inhomogeneously broadened electron-spinresonance lines with width AH >, AH1ss.

Then, in refs. 2-4, kinetic equations were derived qusntum-statistically, these describing the behavior of a tpin system with allowance for cross-rela:<ation prooesses. For the transition probabilities these papers also
led to Eq. (1).

We first consider the motion of an individuat pair of sei+s (Q.= f P) withorr[,allowing for the interaction with the remaining spins. suppose that two spins have different Larmor frequencies &rl amd c,.r2, are coupled by the dipole interaction, and are characterized by the Hamiltonian

in (l) is determined by the lnteractions of the flipped spins with all the remaining eplns of the macroscopic system, and its calculation is therefore a lry difficult problem which has not yet found t satisfactory solution. In a number of papers (see, for
The form of the function g(co)

8rz:

Dor1S1,

fuzSz,

fiDr2srrsr,

ftatz(Sr+Sr_

* Sr_Sr+). (2,,

From the equation of motion for the density matrix p(t) we obtain by a standard device (see ref. g, Chap. g) the following system of equations for the mean values:
or (t)

, b metbod of moments (the possibility of such an investii grtlon was pointed out in ref. 1). In this method, however,
because

oremple, refs. b_and 6) this function was investigated by

of tire observed resonance lines ,3r{9} and g2(ro) of the spins of the first and second species, ,';ilod.$ant8 for the determination of the form of g(co) sug,,.tld that spin flip could occur for only those spins for .,"!hlch the frequency difference co!2 is compensated by the ,,'$$rence of the local dipole fietds resulting from the in... .,'fpctton witb other spins. '' ..ft]1
"

' ;bI means of a convolution

calculate onfy the second and the fourth moment, -which, rs Tas noted in ref. ?, do not enable one to determine the form of g(ar) sufficienily reliably. In ref. L it was sugSested that the form of the function shoul.d be estimated

of great mathematical difficulties, one can in fact

- Tr {p (r) Sr,}, a2(tl:Tr {g (r) .g3,}, I ?rr(t):#lr {p {l) a12 (.9s*.S2- - Sr-,9r+)}, I I anr.):ft Tr (9 (r) a12 (S1aS2- Sr-Sr*)),
'_
J

,r,

which has the same form as the equation of motion of an effective magnetic moment p with components P'

:2 I

1fi (c1

(l)

-ar (f)), p":Itor*n(tl,

F1r

:Tia'cu (r)

(4)

in an effective field H with the projections


0rrr E,:?,

H,:?

2d,

Er:o,

(5)

S(&r) by Grant's method or by means of in&tlcorresponds to the simple physical asi*ilwotutlonl 0'on that only pairs of resonance spins can participate ' -- --t. IS cross-relanation process. Such an assumption is when one requires of the spins that their F }.tonable relative to the constant magnetic field change f o\rer a time T2 Tz = hHlocl-r [7Hlo"l-l (whereHt.,r,= lwhereHloc= c le the mern dipole neta, l, i, tn" strength o}-trc

1;,$f-;i:

Calculation$

i.e., it can

be written in the form

+:-rE

X P'

(6)

The rotation (6) of the effective magnetic moment about the effective field means that during the motion of

the pair of spins some of the Zeeman energy: I ':T


hlip(a1(t)

where

-or (tl'l:tL,H,
a p(t)

o4l=!p-:_ ffi,i,'(r),
, e (q, and hence F, z$l as well are random f of the time. To determine the systematic variation of i p's$l due to the loss of energy by the pair and the relaxatiotr process, it is necessary to average p,ts(tl o all realizations of the random process (we denote this averaging by (. ..)), i.u., to go over in Eq. (?) to ( p,r(tl)i, In our case ( 4z >, 'yHloc), F,z$l will vary insignific*rfi over times of the order ol the correlation time T3 of tho
i
,
i

ergY:

is transferred periodically to the transverse dipole en-

Er:

hZalz?rz(tl:

pr|,

and back (the total energy being conserved):

E -tz:

-JT
I

har2 (a1

() -

oz

(\ {

2fia1"3,2 (r)

: pE.

However such a periodic process will occur only as long as the external magnetic fields acting on the spins of the pair do not depend on the time. tn a real crystal, a definite eontribution to these fietds will be made by the dipole-dipole interactions, and this contribution will depend on the orientation of the spins surrounding the considered pair. Under the inlluence of spin-lattice or spin-spin interactions these orientations will change randomly, as a result of which magnetic fields that depend randomly on the time will arise at the spins of the con-

random variable d(t), and therefore the equation for ( p,z{tl) cen be deduced from Eq. (?) by the method al_ rea.dy used9 to derive the equations of relaxation of the magnetization, i.e., (ltz$)) for the real magnetic mo
Using this method, we obtain
d

Z; <t'i (t)): -2,or"(r,l

(t)),

in which

sidered pair.

Iier to explain the mechanism of phase firmo1y.10,11 The longitudinal dipole field from the spins of the environment enters the equation of motion (6) for the pair in the form of the time-dependent difference of the fields at the spins of the pair Ar2{t), where ,12 is the pair not related to the dipole-dipole interaction t\tztr;l/y is of the order of the mean dipole field H1os, whereas for the majority of pairs ar!, -lg >>yHlocJ. Because al, depends on the time, energy is fransferred from the pair to the remaining spins of the system.

In the case of magnetically dilute crystals with strongly inhomogeneously broadened lines the spins in the environment of the pair will in practice all precess with essentially different frequencies, as a result of which the magnetic fields produced by the transverse components of these spins will be zero when averaged over the time. Therefore, the comparatively slowly varying tongitudinal components of the dipole frelds (essentially, these fields rnary over the time of the spin-lattice or spin-spin relaxation) will lead to the transfer of energy from the pair to the other spins of the system. Such variatiofrS of * the dipole fields at individual spins were considered ear-

where,lt = trhlz + 4a12, and


G

(t,

:(* {l,.,,,, -',, ",}ry).

cr(t)l Iot g{a- x l/Zfiy(at(t) - dz(t}l when rlz t, a12, &d ---Qrerefore the difference between the polarizations of the

Since the energy of the pair is p, zH, z, it follows (9) that over a time - (*rz)-1 the pair eneigy is transferred to the surrounding spins. But Er2 x L/2fic,.rlrtar(t)

spins in the pair vary over the sasre time, i.e., w12 mines the probability of the cross-relaxation process for

this nonresonance meehanism.


In our case c.r!2 >>Arz(t) , e!2, and therefore 66; * 4, and to estimate the orders of magnitude we take G(t) = exp {-t/te}; tben from (11) we obtain for the cross-

ation probability

(air) Ts ^o ut2-2"1,ffi i31'9llT.

(12!

It is convenient to solve the problem of energy transfer in a moving coordinate system (see rel 9r'Chap.2) with zt axis along the instantaneous direction of the effective field H, in which Etz = lt,zF,z (where !,2 and Hts are the projections onto tbe zr anis). The trarsition to such a coordinate system is made by the substitution p's: Ps, p'r: l"rcos 0 (t) * rrsin0 (tl, ttl:-p, sin 0 (t) + p, cos 0 (t),

where 0 (t) is the time-dependent angte between the a:<es z alcid zr, this being determined by the relation cos 0(t) = arr(tl/ci1t), md 6'$| = ulrltl * q*12. Making this transition and expressing F'y and p'x in the resulting equations in terms of liz, we obtain

t+:-61r;j-,{j

ru,,o,,lti(r,)rr

g,tdt,,

(?)

In deriving (13)-(16) we bave assumed that Azana i vary slowly over times of order T3 >> (rlr)-t. Otherwise, when the frequency difference ehanges discontinuously [i.e., over a time < 1co!r)-tl at random instants of time remains constant between these jumps, e(t) in the cal tion ofthetimeintegrals will be proportional to 6(t), and, therefore the rapid oscillations in time in the integrand become unimportant and do not reduce the value of the i tegral, in contrast to the first case. This difference is due ultimately to the fact that the effective magnetic mo-' ment (4) does not suceeed in following the effective field j (5) in the latter's instalt4neous variations. But if the magnetie moment does not follow the field, then one can consider transitions in which a1(t) - dz(t) changes in a fixed coordinate system, as Horvitzlz did using time-dependent perturbati.on theory.
V. E Zobqv and V. N. Provotorov

Sov. Php. Solld State, VoL 1?,

No

5i

Horvitzts result for the cross-relaxation probability a pair of spins when there are discontinuous changes ;of tbe frequency difference between the values co!, +A wltb mean frequency R of the jumps has the form (in our
notation)

termined by the minimal root (-p*in) of the denominator of (15b). When t >>R, we have
("r (t) cr (t))

(o, (0)

c, (0)) exp

(-p,rot),

(17)

where

torr:ifif]i@t@.
ir:
The

hl,

pnro

tu?2R

Atft

IBi- B,o- @il" * Btrol,

(18)

(13)

in which B'1 and Br2 8r the values of 81 and 82 for s = R, and B1s and 826 are the values for s = R and q(Arz) =
d(Arz).

result (13) has been obtained by means of peri;:-, turbation theory, although for a model of motion as simple ,iiir as uncorrelated jumps of the frequency difference the prob,-i, lem of the motion of a pair of spins can be solved rigorlarge and small values of o.r!2, even when 'r. ously for both
perturbation theory cannot be used.

To obtain a concrete result, we take #tl in the form of a rectangle with half-width A = THloc:
(ltr) :

'

For suppose the frequency difference [or rather the part Ar2(t)l varies discontinuously, its value after the jump A12 being unconelated to its value A", before the jump, and that the probability that A.r2 is realized is determined by the relative fraction of states with such frequency difference g(Arz).

*, .lg-A(Ar:(.lz*A 0, Ar, ) .l: * A, Atr (.?r -

J.

Restricting ourselves in the expansion of B11 and B'2 in the small quantity L2/@1i2 to the largest terms, we obtain from (18)
wn:| T2A2R Prarn t T "it iff.
(1e)

The distribution function q(Arz) is determined by the real positions of the external spins, and therefore its u, form can be readily determined qualitatively in any con' crete case. This must be appreciably nonzero only over the frequency interval A yHloc. To specify the time .' variation of a random variable one must also introduce the mean frequency R of jumps, which in order of magnip tude must be equal to the proba"bility of spin-spin or S;spin-lattice fl.ip of the spins that produce the dipole field $qat the pair. F] Since the equations of motion (6) of tbe pair and the :., equations of motion of a magnetic moment are the same, ,*,;our problem now reduces to that of the motion of a spin ierh discontinuously varying longitudinal field, and it can solved by tbe appropriate methods.ls't{ [r refs. 13 and f,be " 14 the stationary solution of the analogous problem was i.considered. We are interested in the nonstationary bebavior. Performing calculations similar to those made ref. 13, for the Laplace transform of the difference of the polarizations averaged over all teaLlzatilons of the ran:dom process we obtain [for 612(0) = 0, o12(0) = 0]
or (p)

It can be seen from (17) that during the motion of the pair the polarization difference changes appreciably over a time [p*io]-t, i.., pmin determines the cross-relaxation probability
w12.

Comparison of (19) and (13) shows that the asymptotic frihaviorJglz tta, a12')-ef the rigorous solution leads to the same rbsult as perturbbtion theory lthe difference in the numerical coefficient is due to the different choice of
q(A12) l.

0. For symmetric distribution


(16), 82 = 0 and (14) becomes
or(p)

We now consider a different interesting

case: olz

firnctions, according to

-er(p):ffi

(zr(0)-ar(0)).

(20)

In the simplest case g(Atzl = L/Z[d(Arz + A)

6(4rz

-A) I we have
cr (p)

u: (p)

: j "-rr,", (r) -or gl>itt -(cr (0) -',

(0))

ff;i,

(14)

or (p)

:tO=n#%

(41

(0)-c2(0))- (21)

F):lr - 81(Rr+4"ttl [s -.R8, (s'* 4o?Jl + BZR(sl? * 4air), (15a] 9b)-[p * arR (tuiz- pr]l {s - BrR (tulz* s')l + B2$"?r- sp) Rt,(15b) whichs=P+R,and
t1

The roots pt, p2, pr of the third-degree pollmomial in the denominator in (21) can be calculated by, for example, Cardan formulas. Then the variation in time of the polarization will be girren by the e:presslon
(221 c1 (0)) [creP,' * "ret't * "rrPJ]. In general, cumbersome expressions are obtained for the roots, so that we give the result for two limiting cases, restricting ourselves in (22) to the terms with largest amplitude and retaining the largest terms in the e4pansion in the arguments of the exponentials.
dr (r)

q (t):

(dr (0)

81

t (.)

-j Br-

-l
ct

t2

4oi,

* ('lg *.)t f
ro)

tu,

,r.^\ [ro'

I
-o

qe:ffiqftjrd,'.

9 (ro) (ro!s

For

Ra12

>t A2(R
(t))

I anl

we have
"rp

The inverse Ia.place transformation for (14) cannot performed, although fOr c,l!, )>L, atz one can find the

(o, (r)

ar

= (a1 (0) T

or (0))

{- &

lrl
(23)

vior of (ar(t)

oz(t)) for large times, this being de-

xco"{2,,t(t.*ft')}.

For Rar,
(o, (r)

<<

Az(ar,

A)
c, (0)) exp

a, (t))

= (o, (0) -

t-

^ffi

11.

(241

We now return once more to the base of large fre_ quency differerices, c,{z >> yHloc. Comparing (1g) and (12) with (1) and noting that for the flip-flop process lVrrl, = al2, we obtain for the considered nonresonance cross-rela:cation mechanism g(c.,!2) x znzR/J(rh)4 for a discontinuous change in the frequency difference and g(c,rl2) * Z(i\). tT3&rl/61-1 for a slow continuous variatiou.

so hold.20,eb

(71. Because of the complete identity of Eq. (6) and the equatioh of motion for the real magnetic moment for the motion of a pair [i-e., for the effective magnetic moment (a) in the effective field (b)l the adiabatic theorem will al-

This theorem has an interesting consequence. If the frequency difference @n is varied slowly (6n u2olzl from the value @rz(0) )>afl to the value -orz(0), then p (seeUq.l which always follows from H(see Eq. S), flips, and this means that both spins flip, Le.,

As a rrrle, the resonance mechanismlrs gives a


stronger dependence on co!2, since targe dipole fi.elds are needed to compensate large frequency differences. Srch fields can be formed for a definite arrangement (orientation) of a large number n - rlr/yH1os of spins in the environment of any pail, but the probability of this arrangement is proportionalls to exlp{ -n2}, and therefore in the resonurnce mechanism the probabi.lity of cross relaxation between two lines must decrease with increasing frequency differenc" ,1, between these lines as exp {-(,':lz-/vHlod2}.
.

such

proc",:-

spin dlmamics; for

if

its flipping will be accompanled, in accordance with


flipped spin.

in rhe ;;l;;';;l?, ""," slowly, some spin flips sufficiently


the

adiabatic theorem, by the flipping of two other spins that interact with one another, one of them being next to the

pairs), we obtain

With allowance for the nonresonance cross-relaxation mechanism, which also occurs in homogeneous systems consisting of spins of two species, the form of the asymptotic behavior is different. Going over from the probability of cross relaxation between two spins wii (1), (19) , (LZl to the probability of cross rela:ration betweeh two lines W12 (this transition can be madet-8 by summation over the

\at-b"-b.rg*,
LL4, 445 (1959).

S. Shapiro, P. S. Pershan, and J. O. Artman, Phys. Rev..

'ili.

Prouotorov, Zh. Eksp. Teor.


(1962)1.

3f

r5,611

Fiz., 42,882 (1962) [Sbv. Php. -

JETP.

aL.

L. Suirhuili. lr.1. D. Zviad,adze, and G. R. Khutsishvili. Zh. Eksp. Teor. Fiz., &,8?6 (1968) [Sov. Phys. - JETP, 27, 469 (1968)].

t. Eiishvili and N. P. Giorgadze, teoi]Ilar. Fiz., L2, 420 (19'i2).

w,,:#)
i, i
.

oi,et l,l.

fctr. Kopviltem, Fiz. Tverd. TeIa,2, f 829 (1960) [6v. Phys. - Solid State,2,1653 (1961)1. 6tt. Hirino, J. Phys. Soc. Japan, 16, ?66 (1961h l?, ?88 $962). tW. J. C. Granr, phys. Rev., rSS. IZ:,5S ftg64). tw. J. cr"nr. Phys. Rev., 134]f354 (1964,; 134, 1565 (1964). sA. Abr:rgam, The Princiffi of Nuclear trta@tism, Oxford (1961), Chaps. II and VIII.
roJ.

fu.

rlA. D. \,lilov, K. lvt. Salikhov, and Yu. D. Tsvetkov. Zh. Eksp. Teor. Fiz.. When olz - yHloc, the frequency difference can be easily compensated by dipole fields, i.e., the resonaaEb \ ..63, 2329 (19lQ)-_[Sov. phys. - JETp, 36, 1229 (i9?3.1.l'tp. Horvirz, liiiy"-a"u. (B,r, 3, 286? tr9?lr. mechanism that proceeds through resonance pairs will r3A. I. Burshtein. Zh. Eksp. teo]. riz., 54, 1120 (1968) [Sov. phys. - JETP, predominate in the cross relaxation. Conversely, when 21. 600 (1968)1. ,\z>r yHloc, there are few resonance pairs and the non1{ l,t. Salikhov and A. B. Doktorov, in: Paramagneric Resonance , Lg44re sonance cro ss -relaxation mechani sm, which occur s i n all pairs and gives a power dependence of W,2 on the fre-

R. Kaluder and P. W. Anderson, Phys. Rev., 125, 912 (1962).

ltc.

1969

lin

RussianJ, Kazan (f 970),

4.2, p. L22.

quency difference,

will predominate.

It is interesting to note that in some experimeng"l6-19 at large frequency differences a transition from a Gaussian dependence of the cross-relaxationprobability on the frequenc)' difference to a weaker, possibly power dependence was noted.

W. Parker. Amer. J. Phys.. 38, 1432 (19?0). rtF. L. Aukhadeev, I. I. Valeev, L S. Konov. V. A. Skrebnev. and \1. A. Teplov, Fiz. Tverd. Tela, 15, 235 (19?3, [Sov. Phys. -Solid Srate, 15,
163 (19?3)1. l7O. Takashi, K. Tatsuo, T. Toshihiko, and S. \litsuo, Solid Stare Commun., 13, 643 (19?3). lEvon R.?remer, Phys. Status Solidi 42, 507 (19?0). , reY. Tokunaga. S. Ikeda, K. Ito, and ilHaseda, J. Phys. Soc. Japan,35. 1353 (r9?3). zoF. 81och, Phys. Rev., ?0, 460 (1946).

In conclusion we return once more to Eqs. (6) and

U2

So,. Phyu Solid State, VoL 1?, No

V. E. Zoborr and V. N. Provotoror