BLOCH EQUATIONS WITH DIFFUSION TERMS FOR

ROTATIONAL MOTION IN FLUIDS

I. S. Donskaya and A. R. Kessel' UDC 538.113

The phenomenological Bloch equations for magnetic r e s o n a n c e a r e supplemented by t e r m s

f o r rotational diffusion in fluids. The equations a r e used to d e s c r i b e damping of m a g n e t i z a -
tion components and the line shape of nonresonance absorption in parallel fields for ions with
an a n i s o t r o p i c g f a c t o r and an effective spin of 1 / 2 . In both c a s e s , the contributions of the
diffusion t e r m s a r e c o m p a r a b l e to the contribution f r o m longitudinal and t r a n s v e r s e r e l a x a -
tion t i m e s (T1, T2).

I . T o r r e y [1] f i r s t drew attention to the fact that the Bloch equations in magnetic r e s o n a n c e , which
allow for diffusion motion only in kinetic coefficients, do not c o m p l e t e l y r e f l e c t the effect of diffusion on
the dynamic b e h a v i o r of magnetization, and he supplemented these equations with s e m i c l a s s i c a l t e r m s
d e s c r i b i n g the change in magnetization due to translational diffusion. The B l o c h - T o r r e y equations ef-
fectively and c o m p a c t l y d e s c r i b e magnetic r e s o n a n c e in spatially inhomogeneous media: for example,
damping of s p i n - echo amplitudes in fluids by applying a magnetic field g r a d i e n t [1, 2], and magnetic
r e s o n a n c e line shape of conduction e l e c t r o n s in metals [3, 4].
Recently, Zatovskii and F i s h e r [5] employed s t a t i s t i c a l mechanics methods of i r r e v e r s i b l e p r o -
c e s s e s to obtain the t r a n s p o r t equation for magnetization, and f r o m this equation the B l o c h - T o r r e y equa-
tions w e r e obtained as the l i m i t for a fluid medium with an i s o t r o p i c diffusion coefficient. The quantum-
s t a t i s t i c a l a p p r o a c h , b a s e d on the F o k k e r - P l a n c k equation, to the description of the effect of diffusion
on magnetic r ~ s o n a n c e p r o p e r t i e s was d i s c u s s e d by K o r s t - K h a z a n o v i c h [6].
All the p r e v i o u s p a p e r s on the B l o c h - T o r r e y equations r e f e r to t r a n s l a t i o n a l diffusion. In the p r e -
sent p a p e r , the Bloch equations a r e supplemented by t e r m s d e s c r i b i n g rotational diffusion. T h e s e t e r m s
a r e introduced by a s i m p l e c l a s s i c a l method and the changes they produce in the d e s c r i p t i o n of magnetic
r e s o n a n c e a r e d i s c u s s e d . The b a s i c a i m of this p a p e r is to e s t a b l i s h the i m p o r t a n c e of these changes.
The q u a n t u m - m e c h a n i c a l derivation of rotational-diffusion t e r m s in B!och equations can be c a r r i e d
out by a method s i m i l a r to the one used in [5]. However, it is likely that such a derivation would not
qualitatively change the r e s u l t obtained h e r e by the c l a s s i c a l method, as is the c a s e for translational dif-
fus ion [5].
2. In o r d e r for diffusion to affect magnetization, it is n e c e s s a r y that the energy of the magnetic
p a r t i c l e s be changed by the diffusion motion. In the c a s e of t r a n s l a t i o n a l diffusion, this is attained, for
e x a m p l e , by application of a magnetic field gradient. F o r rotational diffusion to a p p e a r , it is n e c e s s a r y
that magnetic e n e r g y depend on p a r t i c l e orientation. Such c a s e s a r e f a i r l y common: p a r a m a g n e t i c c o m -
plexes with an a n i s o t r o p i c g f a c t o r or with fine splitting, nuclei with quadrupole m o m e n t s in the e l e c t r i c
field of a n o n s p h e r i c a l molecule, d i p o l e - d i p o l e n u c l e a r interactions in m o l e c u l e s , etc.
We c o n s i d e r a p a r a m a g n e t i c p a r t i c l e in a complex or molecule having an axis of s y m m e t r y r. Let
the angles 0, r give the orientation of the r axis, and the angles ~, fi the orientation of the magnetic
m o m e n t of the p a r t i c l e with r e s p e c t to the magnetic field (the z axis in the l a b o r a t o r y coordinate s y s t e m ) .
We introduce the angular density of p a r a m a g n e t i c p a r t i c l e s nc~fi(0, ~) and the angular density of m a g -
netization M(0, ~) then

Kazan Physicotecbnical Institute of the Academy of Sciences of the USSR. Translated from Izvestiya
Vysshikh Uchebnykh Zavedenii, Fizika, No. I, pp. 42-46, January, 1973. Original article submitted
July 5, 1973.

9 19 75 Plenum Publishing Corporation, 227 West 17th Street, New York, N. Y. 10011. A,%)part o f this publicatiolz l~tav be reproduced. I
stored in a retsqeval system, or transmitted, in any fi)rm or b), an), means, electronic, mechanical, photoe~pvinr mic'r~filmin,~,.
recording or otherwise, without written permission o f the publisher. A C~)l)y o f this article is a~,ailab!e~'(Jm the publisher J}~r $I5. O0.
{
J
29
 j'n<,, (0, ?) d.q~.d~2o., = N; Mz (0, ?) = p S n~ (0, ,?) cos ~ d ~ ,

where g is the magnetic moment of an individual particle; and N is

t h e i r total number. Then, magnetization of the angular spin packet is
6M(0, q0), i.e., magnetization of all molecules whose r axis is in the
solid angle dg0, 9 is equal to 6M(0, ~o) = M(0, ~0)d~2060.
Rotational diffusion of molecules leads to a flux vector r through
the boundary of the solid angle (Fig. 1). We write the flux c o r r e s p o n d -
ing to the rotation with a variable angle 0-
Fig. I. Vector flux through the
fi, ~; ~ (0) = 0%~; ~ (0) n~ (0, ?) -- D w n ~ ~ (0, ?), (1)
boundary of the solid angle d~0,tp
for rotational diffusion of m o l e - where Wo~,fi; ~o is the rate of change in orientation along 0 due to con-
cules. servation f o r c e s associated with potential energy, D is the diffusion
coefficient, and V0 is the 0-component of the gradient in spherical
coordinates.
Following T o r r e y [1], we take as the speed wa,fi; ~0 Einstein's relation wa,fi; ~0(0) = - ( D / ~ T ) V 0 u ( a ,
/~; 0, @. H e r e , u(a ,i3; 0, @ is the potential e n e r g y of a paramagnetic p a r t i c l e in a molecule. A s i m i l a r
e x p r e s s i o n is obtained for the flux Ja,fi; 0@) corresponding to a change in the angle ~0.
The change in the z component of magnetization of angular spin packet due to rotation is

a~kl~ (0, p) = d~p (~ cos ~.j~. ~;~ (~) d~~ ~= pj~ (O) dy,
(3)
d~M~ (0, ~) 0...... t = sin OdOp f cos ~j~. ~;~ (,~) d~ ~ = l~j~(?) sin OdO.
dt u

L e t nP/3 (0, ~0) = c exp l\ u uT "' ~) \] be the equilibrium angular dens ity, and 5MP(0, ~0) = dg0~v/s

cos c~nPfi(0, ~o)dgta$ be the equilibrium magnetization of the angular spin packet; then with u(a, fi; 0, r
<< t{T which h e r e a f t e r we a s s u m e to be valid, we have

~MP"(0' ~) = -- d~ tcTPC.i cos ctu (~, ~; 0, ~)

d~2~,, (4)

KI 0

We calculate the change 6Mz(O, @ due to the flux vector r through the boundary l of the solid angle d~-t0q~
on a s p h e r e of unit radius; for this r e a s o n we substitute the expression for the e l e m e n t a r y fluxes (1) into
(3) and integrate o v e r the contour l:

o~mzat(o,~) = D f atv I~M~(0, ~ ) - ~Mz(0, ~)]. (5)

l

The t e r m with 6MP(0, ~o) in Eq. (5) is due to the angular speed (2). When obtaining it, we a s s u m e d that the
equilibrium angular density equalled

n~(%'9) = C [ 1 - ~'(~'~;
~cT 0''~1
' 7' ... 0 ( ~ r ) -~- ] ,

w h e r e ul(c~, /3; 0, q~) is some function of the angles a , 13; 0, ~owith an o r d e r of magnitude equal to the po-
tential energy u(c~, /~; 0, r in the approximation linear with r e s p e c t to 1 ~toT, t h e r e f o r e , the c o r r e s p o n d -
ing t e r m in (5) is equal to (4a).
Using Greenvs equation to calculate the c u r v i l i n e a r integral (5) over the e l e m e n t a r y contour, we
obtain
0_~ Mz(O ' ? ) = D5o, ~ [P~MPz(O,? ) - 8.Mz (0, ~)] P~S,
Ot

30
where A0,~0 is the Laplacian on the surface of the sphere, and 58 is the area bounding the solid angle d~0q0.
Therefore, we have
c).% (0, ~)
- D,3>= [M~ (0, '9) --M~(O, ,.~)]. <6)
8t
It is a s s u m e d h e r e that the diffusion c o e f f i c i e n t is i s o t r o p i c .
T h e e n t i r e p r e c e d i n g d e r i v a t i o n can be r e p e a t e d f o r the o t h e r m a g n e t i z a t i o n c o m p o n e n t s . The change
in Mx(0 , ~0) and My(0, ~o) due to diffusion is a l s o given by r e l a t i o n s of the f o r m of (6).
The s y s t e m of B l o c h equations d e s c r i b i n g the change in m a g n e t i z a t i o n due to r e l a x a t i o n p r o c e s s e s
and m a g n e t i c field i n t e r a c t i o n should be s u p p l e m e n t e d by the diffusion change in m a g n e t i z a t i o n (6), a l -
though with a sign that d e c r e a s e s the total m a g n e t i z a t i o n :

- - = -; [ ~ / . : H]~ M~,~.. - - Af~" -4-

, D-~ ( M ~ - - M p~
. ...... ~,,.. (7)
8t T=
H e r e , T z = T 1 and T x y = T 2 a r e the longitudinal and t r a n s v e r s e r e l a x a t i o n t i m e s , and MP is the e q u i l i b r i u m
a n g u l a r d e n s i t y of m a g n e t i z a t i o n . In (7), t h e r e is no explicit functional d e p e n d e n c e of M on 0, % and t.
We note that the diffusion t e r m s in (6) w e r e obtained without a s p e c i f i c f o r m of the potential e n e r g y ;
t h e r e f o r e , Eq. (7) can be u s e d to d e s c r i b e d i f f e r e n t e x p e r i m e n t a l s i t u a t i o n s .
3. As an e x a m p l e , we c o n s i d e r a c o m p l e x at the c e n t e r o f which is a p a r a m a g n e t i c ion with an ef-
f e c t i v e spin of 1 / 2 and an a n i s o t r o p i c g f a c t o r , i.e., we c o n s i d e r a situation c o r r e s p o n d i n g to the M c C o n -
nel r e l a x a t i o n m e c h a n i s m [7]. The effective field acting on the m a g n e t i c m o m e n t in l a b o r a t o r y c o o r d i n a t e s
is H e tf = ~H 0 + >r cos~ + j s i n 0 cos0 s i n e + g(cos2(J-1/3)], w h e r e i, j, ~ a r e the d i r e c t i o n a l
unit v e c t o r s of the l a b o r a t o r y c o o r d i n a t e s ; ~< = A g / g ; Ag = g l l - g • g = (gll + 2 g • g II, g• a r e the p r i n c i p a l
v a l u e s of the t e n s o r in the m o l e c u l a r c o o r d i n a t e s y s t e m , with Ag << g; ~ << 1.
The Bloch equations in this field a r e

OM=
-- f 6% + % ) , % • f~,,•
at
(8)
8M.~ i (m_M -- ..... M_) ~ , d ~ - - M _ ,
P
' DA(M:--M~).
Ot 2 T~

Here,

c rL ( ,~1']

9 z s i n O c o s g ( Z c o s ~ -i-jsin.9)}, cu+=z%sin0cos0e•
Y

w h e r e cc0 = 7H 0 is the L a r m o r f r e q u e n c y ; and M0P = Ng2H0/3~T is the e q u i l i b r i u m m a g n e t i z a t i o n in the i s o -

tropic ease.
The solution of s y s t e m (8) is sought in a e o o r d i n a t e s y s t e m r o t a t i n g with the L a r m o r f r e q u e n c y in
the f o r m of a s e r i e s of L e g e n d r e p o l y n o m i a l s M~(t) = e• 2CI(t)P/(6) with an initial eondition M p
l
= ~r w h e r e C~ = C~5,c 0 = M~/47r6K0 (~ << 1). The solution f o r the total m o m e n t of the s y s t e m in

l a b o r a t o r y c o o r d i n a t e s to within the f o u r t h p o w e r of the s m a l l p a r a m e t e r e = 2/3~%~'~/D is

M+ (t) = ( M+ d%-- ~::= e-i~

1 (2 3"am~)'-' (9)
1 T* = 1,T._,-- i Ta; Tg 1 -
30 D

The result (9) indicates that the additions of the diffusion terms (6) gives rise to an additive contribution
1 /T 3 to the effective damping rate of the transverse magnetization components. This situation must be
considered when experimental data is used to determine microscopic parameters.

31
 Actually, the longitudinal and t r a n s v e r s e relaxation t i m e s for the McConnell m e c h a n i s m a r e d e t e r -
mined by [9]
TT ' = 3 z ( % % ) T T ' ; T7 ~ = [ l + 3 . 4 z ( % % ) l T 7 ' ,

w h e r e z(x) = (1 + x2)-l; r e = 1 / 6 D . T h e r e f o r e , the r a t i o of the effective relaxation r a t e to the inverse

t r a n s v e r s e r e l a x a t i o n t i m e is ( T ~ ) - t / T ~ t - 1 1 / 7 = 1.57 for rapid diffusion (w0r c << 1) and (T2*)-t/T~ 1 = 2
for slow diffusion (w0r c >> 1, cC0rcX << 1).
4. N o n r e s o n a n c e Absorption in P a r a l l e l Fields. In o r d e r to d e s c r i b e n o n r e s o n a n c e absorption in
p a r a l l e l constant H 0 and v a r i a b l e h(t) = he iwt m a g n e t i c fields, it is n e c e s s a r y to r e p l a c e H0 in Eq. (8) by
H 0 + h(t) and r e p r e s e n t equilibrium magnetization in the f o r m [9, 10] Mp = (• + h a (t)), where •
= N(~2/3~,T) is the C u r i e s t a t i s t i c a l susceptibility. The s t a t i o n a r y solution of this s y s t e m is sought as
M=(f), % t) = Zo4r./4~ ff q-a=(0, ?)e i~t. (10)
Setting ~+(0, ~o) = A_2~-~(6, ~o), ~z(r ~o)= AoY~ ~o) + AzY~(0, ~o), w h e r e Aa a r e s o m e constant coefficients
d e t e r m i n e d f r o m the s y s t e m for ~a and Y ~ a r e s p h e r i c a l functions of o r d e r l we obtain the following e x -
p r e s s i o n for the s u s c e p t i b i l i t y X* = ) / ' - i X " = t / h f ~z(0r 0 =4T{A0/h;

7.* = Zo [1 + z (x, Y)I;

1 + i~oTl
l + x ~_ [ { - - i ( x + y ) 1-gi(x--y)]
(ii)
z (x, y) -
2 -r (x + y y 4-1 + i ( * - - y . J '
~ - toO%; Y ~ tO'~c.

When z = 0, (11) t r a n s f o r m s into the usual value of s u s c e p t i b i l i t y in p a r a l l e l fields. It is significant

that z does not vanish for any values of the p a r a m e t e r s w << w 0 and Tc, Consequently, the diffusion t e r m s
in (6) always e x e r t an a p p r e c i a b l e influence on absorption in p a r a l l e l fields. With rapid diffusion (x, y << 1)
z = 1 and absorption is doubled. The s a m e r e s u l t is obtained when x >>y and with slow diffusion x ->-1. A
d i f f e r e n c e between the field and f r e q u e n c y dependences can be expected at high frequencies co >> coo with
slow diffusion y > 1.
5. The two e x a m p l e s d i s c u s s e d above indicate that the additional t e r m s for rotational diffusion in
the Bloch equations make contributions to magnetization c o m p a r a b l e to that of the relaxation p r o c e s s (T l,
T2). T h e r e f o r e , they m u s t be taken into account when i n t e r p r e t i n g e x p e r i m e n t a l data, and this is also a
r e q u i r e m e n t when p e r f o r m i n g s i m i l a r calculations f o r other c a s e s of e x p e r i m e n t a l i n t e r e s t .
The authors a r e indebted to B. M. K o z y r e v for his i n t e r e s t in the w o r k and d i s c u s s i o n s of the r e -
sults.

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