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Theory of spin-phonon coupling in concentrated paramagnetic salts and its effect on thermal conductivity

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1967 Proc. Phys. Soc. 92 1024 (http://iopscience.iop.org/0370-1328/92/4/325) View the table of contents for this issue, or go to the journal homepage for more

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P R O CP H Y S . S O C . 1 9 6 7 , . ,

VOL.

92.

P R I S T E D i s G R E A T BRITAIIS

Theory of spin-phonon coupling in concentrated paramagnetic salts and its effect on thermal conductivity
R. J. ELLIOTT and J. B. P.4RKINSON
Department of Theoretical Physics, Oxford University .VIS. recezeed 6th June 1967

Abstract. In a concentrated paramagnetic salt at low temperatures it is possible to think of spin excitations with a well-defined wave vector k similar to spin waves, These are coupled to the phonons and result in mixed modes given by the JacobsenStevens relation, These mixed modes are studied by the Green function method of Sears extended to higher order to obtain a finite lifetime of the modes which increases as T increases and the spins disorder. Paramagnetic relaxation and thermal Conductivity are studied in this system. T h e main effect of the spin-phonon coupIing at low temperatures IS to modify the modes; lifetime effects occur in higher order. Comparison is made with some existing experimental data and more detailed experi. ments are suggested.

1. Introduction The interaction between magnetic ions in a crystal and the lattice vibrations is responsible for several phenomena which have been extensively studied. From the magnetic point of view it gives rise to spin-lattice relaxation (cf. Orbach 1961) and in higher order t o an effective coupling between different ions (Sugihara 1959, Orbach and Tachiki 1967, unpublished). The phonons are also affected as has been shown by measurements of their group velocity (Shiren 1962) and phase velocity (Guermer et al. 1964) in MgO containing paramagnetic impurities. The interpretation of this type of experiment was given by Jacobsen and Stevens (1963), who pointed out that the resonant nature of the coupling between the ions and the phonons at the characteristic ion frequencies gave rise to a modification of the spectrum of excitations which became mixed. This description is particularly apt in a concentrated salt where periodic lattice symmetry is maintained and at low temperatures where the disorder in population of the magnetic levels is small. In effect the crystal becomes in these circumstances a sort of ferromagnet and there is a spin-wave branch in the excitation spectrum which interacts with the phonon branch. Sears (1964) has obtained an approximate self-consistent solution of this problem for a general temperature which he used to calculate the form of the specific heat anomaly. In this paper we propose to extend his work and that of Tucker (1965) by improving the decoupling scheme to consider the lifetimes of these coupled excitations at general T. Van Eekelen and Stevens (1967) have recently shown that such an extension removes most of the anomalous specific heat calculated by Sears in agreement with a perturbation calculation which they perform.? The main object of the work is, however, to study the thermal conductivity of such crystals. Orbach (1960, 1962, 1963) first pointed out that this would be a fruitful method of studying the spin-phonon interaction and has discussed in detail the experimental results of Morton and Rosenberg (1962) and McClintock et al. (1967). His theory, however, was primarily intended for the case of a dilute crystal with a low concentration of magnetic ions and regards the resonant scattering as giving rise to a lifetime for the phonons which dominates over a narrow spectral range. For the concentrated crystal we feel it 1s more correct to regard this resonant interaction as modifying the excitation spectrum the actual lifetime effects then occur in higher order. The predictions of the theory are qualitatively similar to Orbachs but differ in some important respects in the concentrated case. I t also avoids some of the difficulties stressed by Huber (1964, 1966) concerningthe

t We are indebted to Professor Stevens and Dr Van Eekelen for discussions of the connection between our two methods which shou,ed that n e had omitted some terms in an earlier version ofthis paper. 1024

Span-phonon effects zn thernzul conductzvzty

1025

form of the spin-phonon line-shape function. A confrontation with experiment should decide the relative applicability of the two methods but is not possible until there are more detailed measurements on a concentrated salt with ions in a simple doublet level. Other scattering mechanisms from boundaries and impurities must be included as unknown parameters unless they can be measured independently. While this work was in progress the lifetimes of the coupled modes were discussed by Mills (1965) who used classical scattering theory and Yolin (1965) who used a diagrammatic technique rather than the Green function methods we employ. Muller and Tucker (1966) have also discussed the thermal conductivity in terms of the coupled modes, though their discussion is less complete than that given here.

2. The Hamiltonian and normal modes T h e model used is the simplest one which will show the effects and closely follows that developed by Sears (1964). There is one paramagnetic ion per unit cell and this is assumed to have only two low-lying energy levels separated by an energy Awe. These levels may be two crystal-field singlets or a Kramers doublet split by a magnetic field. I n either case the two states may be described in terms of a fictitious spin S I = 4. The magnetic ion Hamiltonian may then be written

yes = - 2 fiw0s,,.

(2.1)

The lattice vibrations at low frequency will have three branches with a frequency linearly dependent on the wave vector k. For simplicity we take the isotropic Debye model in which all three branches p are degenerate and wp(k)= wIc= ah. If we define the usual creation and destruction operators for phonons with Bose-Einstein commutation relations

T h e interaction between a spin at R, and the lattice is proportional to the local strain. It has two essential terms, one diagonal in the ion states
n

and one connecting the states

to zero as K

I n the isotropic Debye model A,, = BkP. Since A is proportional to the strain it tends --f 0 as K / w , ~ ~ and it is convenient to define a dimensionless spin-lattice ,

(2.5)
In the Kramers ion because of time reversal E c w;j2, but in the non-Kramers case c cc wo-12. T h e excitations of the spin system are usefully described in terms of spin deviation operators S $ 2 = I2- a + a 13 I s,, = &(a,+a,+), s,= %(a,-*+). t 1 (2.6)

which have fermion anticommutation rules on the same site [a,, U , ] + = [ a t + ,a1+1i = 0 [U,, ai+]+ = 1, but commute on different sites i #j. [ u t ,a,*] = [a,, a,] = [ U , * , a,] = 0

(2.5)
(2.8)

1026

R. J. Elliott and J. B. Parkinson

On the same site the cominutator is an operator

[a,, u l + ] = 2si,. (2.9) Then the Hamiltonian composed of (2.1), (2.2) and (2.4) is quadratic in the a and c

cf ?f

&WO

2 (a,+a,-+)+ 2
k.P

fiWk(ckp+ckp+i)

and may be modified to give coupled spin-phonon modes. Terms which are higher order in the operators llke (2.3) and some others will be considered separately in 5 5 . The properties of the system with (2.10) were studied by Sears (1964) using a Green function technique (cf. Zubarev 1960). .4ny thermally averaged correlation function may be obtained from the Green function. I n particular the response functions at frequency

(J
-cc

,4(t)B(O)etwtdt) = l i r n A { g A B ( c o + @ ) - gAB(u-z$)) (2.11) eBw 1

are related to (2.12) the Fourier transform of the Green function ($4; B ) . Double brackets of this kind are used to denote the Green function and single brackets indicate thermal averages of Heisenberg operators. Q(t)is the step function. T h e properties of B are usually obtained from the equations of motion
d
z&-

dt

1 ((A; = - ([A, B> B])6(t)+(:[A,&];B)).

2n

(2.13)

Sears used this to obtain

G,,(W)

=
-?)

e a l ( t ) ;~ , L ( o ) > > dt. e*at

(2.14)

The equation of motion gives

(2.16)
comes from the commutator (2.9). He then decoupled the last term on the right to gir7e an approximate linear result: <siockp; a,'>> ( S ~ t ) < ~ k . p ; ~'>>. u (2.17) Further equations for these new Green functions may then be derived by a similar decoupling procedure. Because of the translational symmetry it is more convenient to derive

G(k, W )
and (Sears 1964, equation (32))

- 2 G,,(w) exp (zk' (Rl - R J

N
1,)

(2.18)

(2.19)

Spzn-phonon effects in thevmal conductivity

1027

The imaginary part of this at u t i $ which is needed in (2.11) is a set of 6 functions at the zeros of the denominator. These are at I w,(k), where z = 1,2, the solutions of (2.20) 2w2 = W k 2 + W o 2 F { ( W , 2 - ~ W O ~ ) 2 + 4 2 ( 3 W 0 ~ w k ~ } 1 ' 2 , This is just the Jacobsen-Stevens relation and indicates the coupled nature of the modes. T h e theory of the preceding section is clearly unsatisfactory in that it gives coupled modes of zero damping and fixed k which would be appropriate to a system with the full translational symmetry of the lattlce. However, away from T = 0 there will always be a disorder in the spin system and this will lead to a width for the modes even when the Hamiltonian is restricted to (2.10). We should expect this width to be small as long as pw0 $ 1, when the system behaves rather like a ferromagnet. T o study such a width we must improve on the approximation (2.17) in the solution of (2.15). The equation of motion for the new Green function is obtained from (2.13) using the commutation rules for spin and phonon operators. The w transform gives

This is decoupled by substituting for the spin operators in terms of the a's using (2.6) and taking averages over all pairs of operators. These averages are then replaced by their values in the non-interacting limit. Thus the averages such as (u,ul+)(i # I ) and (alckp+) which go to zero as E -+ 0 are neglected in comparison with ( a l a l ' ) , (ckp+ckp) which remain finite in that limit. I n this approximation

+ -Akp dN

(ckp'

ckp >O

exp( - ik

Rt)(Gtj- H t j )

(2.22) Taking equations of motion we (2.23)

where G,, is defined in (2.14) and H,, is <att;U,'). find 4G,,+Hlj)

=
%-

___ + %(G,, -HI,) ( I P I , S 2

which has a simDle form since G,,+ H,, commutes with the spin-phonon coupling term in (2.10). A similar treatment of the other Green function appearing in (2.15) gives

The different treatment of the term 1 = i in both (2.22) and (2.24) arises from the fact that S,,S,, = $iSlgand no decoupling is necessary in that term. The thermal averages of the c operators give n, and nk + 1 respectively where n, is the boson equilibrium number.

1028

R. J. Ellzott and .I. B. Parkinson

Substituting back into (2.15) gives with the use of (2.23) an equation entirely in G:

(2.25)
where

and

(2.27)
Changing ( l / N ) C , -+ 3 J 3 w k Z / w m 3 ) dw, and giving w a small imaginary part leads to real and imaginary parts of R and 0. The Fourier transform of R is

1
S L

1 R(k) = - 2 RZI exp(ik . (R, -RI)}

E2WOWk2

t,i

w2

- wk2

+ R,'

3irre2wOw3 2w,3

(2.28)

where R,' is a principal-valued integral. T h e last terms arise because R,, = 0 :

R,'
For
w

wm3

3E2Wo

< omthis is approximately given by the first term. 0 has a similar form
(2.30)

s, mWk4dWk

(2.29)

and the principal-valued integral

So' can

only be evaluated analytically at T = 0 when

(2.31)
At small w this may be neglected with respect to Ro'. Under these conditions the solution of (2.25) when Fourier transformed is G(k, U ) = 2rr (w2where
0
(U

+WO)(W2--k2)+gE2uwOW2--(w2-wk2)X
wo2)(w2

- w k 2 ) --E2u.W0202-22iw(w2- wk2)r

(2.32)

(2.33)
and

(2.34)
T h e poles, given by the zeros of the denominator, now occur at complex frequencies corresponding to widths. Leaving a detailed discussion of these till later it may be noted that the denominator of (2.32) leads to a dispersion relation different to (2.20). I t may also be written {wZ-(l s ~ ~ ) w o ~ ) ( w ~ - w k ~ ) - - E ~ u ~ o ~ w , ~ (2.35) =0 whose solutions we designate w , ( K ) , a = 1, 2. As k + 0 the two solutions are w1(k)2 = wo2(1+'U), w2(k)2= wk2(1- I - - E ~ ~ ) - ~ .

(2.36)

Spin-phonon effects zn thermal conductivity

1029

The second is dominantly phonon-like with a changed sound velocity. T h e first is spinlike and shows a shift from the resonance frequency w o . At large K , w,(k) becomes spin-like and w,(k) - + W O . q ( k ) moves to high frequencies so that the approximation forms of (2.29) and (2.31) are no longer valid. The actual form of these expressions depends on the assumption of a Debye spectrum but it indicates that w,(k) + wlc in this limit. These are different from Sears result using (2.20), where it was found that
w,(k) =
W , ~ + E ~ U W ~ ~

and

w,(k), = wo2(1+U).

The shift in w, over the large range of k was basically responsible for his anomalous specific heat and the better decoupling scheme removes this anomaly. The self-consistent equation for o obtained by Sears from G,, now gives the uncoupled value tanh(@wo). (2.37) T h e generai shape of the new dispersion curves is shown in figure 1 and is essentially unchanged except for an upward shift of $ E ~ G C L J ~ . There is a gap in the spectrum of coupled
U

.
0

w*

1%

Figure 1. T h e Jacobsen-Stevens dlsperslon relation for E*G = 0.1.

modes although this is spanned by the other phonon branches. In the strongly coupled cross-over region the minimum separation is (2.38) u,(k) - w,(k) = 2 c u 1 @ ~ 0 2 .

It is convenient to have a quantlty to characterlze the different amounts of spin and phonon character in the modes. We define for thls purpose
fs =

u,2(k) - wj2(k)
fs+fp
= fs+fp

WL2(k)

-u k 2

,
=

u,(k)-(l
WZ2(k)-

+~~u)wO
W,2(k)

(2.39)

Using (2.35) it is readily seen that

= fs+fs = fp1+fp? =

1.

(2.40)

1030

R. J. Elliott aird J. B. Parkinson

3. Specific heat
The thermal conductivity K of a dielectric solid is given by the simple Boltzmann equation method (Klemens 1955) as
K

4-C cl(k)Sl(k)ilt(k)
tk

where the sum is over all modes k and branches i. Here il,(k) is the mean free path of the mode. I t is sometimes more convenient to use the inode 'L\ idth (inverse relaxationtime) y,(k) where

This simplified approach is adequate for the model with xhich we are working. The group velocity can be obtained from the dispersion relation and, to second order in E,

This does not depend on fs, which seems reasonable since the unperturbed spin modes have zero group velocity. In this section we shall be concerned tiith the calculation of S,(k), the specific heat associated with each mode. It is simple to derive U,(k), the contribution of each mode to the thermal energy, and then differentiate with respect to T. The coupled spin-phonon modes give a contribution from each of the terms of ,R. Rewriting (2.10) as
??e

2 {fiUg(aktak-$)f
k

c fiwk(Ckp'Ckpfi)f
P
1

2 Akp(CkpfC-kp+)(akfa_k')}
?

where a, = n;-1/2

2exp(zk

'

Rib,

(3 -4)

we can pick out the parts belonging to each k. (ak+ak) is related to G(k, w ) of (2.19) by (2.11). It is also necessary to calculate the Green functions appropriate to the other terms in (3.4). Fortunately these can be related to G by exact relationships. For example (w-Uk)<ckp;
st'>

2Ak,exp(ik.R,)(G,,+H,,)
3

(3 *5)

which, together with the equation for ((ckp+;S,")), gives the cross term in (3.4)

when terms in e4 are neglected in the numerator. We have used the exact relations (2.23) and (3.6) and the approximate form (2.32) for G, neglecting the imaginary parts of numerator and denominator. Further relationships relate Dpp(k,W) = <ckp; ckp+>> G. For to
+

(0 -

w,)Dpp(k,

w) =

(2,)

+ Akp <ak + akf ;ckp >

(3.7)

which may be related to (3.5) by taking complex conjugates

Spin-phonon effects in thermal conductinity

and using (2.23) and the approximate form (2.32) gives

1031

The first term corresponds to the two unperturbed phonon branches. The last terms in (3.9) and (3.6) have poles at the frequencies of the coupled modes given by (2.35). The imaginary parts of those Green functions are delta functions S ( W & W ) for = U,<,w,(k) and w,(k) which are to be used in (2.11). For the two unperturbed phonon modes we obtain

where ,d = lz/k,T. This is of course the standard result. The strength of the poles at the coupled-mode frequencies is conveniently written in terms of the quantities f defined in (2.39) which measure the amount of spin and phonon character. For G in (2.32), neglecting still X and r, the pole strength at w,(k) is (3.11)

(3.12)

using (2.35). Adding the contributions from

w,(k) using the relations

= -1
=

(e4m-l)-l+(e-pm_1)-1 (eBW-l)-l-(e-flu- 1)-l one finds after some manipulation

(3.14)

coth(@w)

In addition there is the zero-point energy ;h(w,- w o ) from (2.10) which should be divided between the coupled modes. The theory does not give a unique way of effecting this division but the spin and phonon weighting factors (2.39) suggest (3.16) B~fpi~k-f&0).
The total contribution to L:,(k) may then be written

Udk) __
Tz

- +f,Zw,(k) coth{+,(k)}

1032

R. J. Elliott and J. B. Parkinson

I n this form the separate phonon and spin are recovered for i = 1 and 2 respecti\,elv when E -+ U. An approximate form of (3.17) is found by noticing thatf, is small unless w,(k) 2: Then U,&) __ N 4f:Wk COth(4PWk) $ 4 f s a W o tanh(@wo) (3.18)

i.e. the unperturbed spin and phonon specific heats weighted with thef's. This is similar to the method used by Muller and Tucker (1966). We have found that (3.15) gives results which differ markedly from (3.17). Ne\-ertheless, it might prove a useful approximation in more complicated systems. In taking the derivative of (3.17) with respect to T it must be borne in mind that w,(k) depends on T through CJ which is given consistently to this order of approximation by (2.37).

4. Mode widths The thermal conductivity is also controlled by the damping of the excitations as defined by (3.1) and (3.2). T h e imaginary terms in the denominator of (2.32) correspond to such a damping which we refer to as the intrinsic width. I n addition the true Hamiltonian will contain further terms which are not of the form of those in (2.10). We have considered the possible forms of these, but because of the complexity of the calculations we have normally estimated their effect on the widths by appeal to perturbation theory and a knowledge of the contributions they give in the uncoupled case. 4.1. Intrinsic width Following Galitskii and Migdal (1953) we write the denominator of (2.32)
[{U

- iYl(kN2- W m 2 1 [ ( W

- iY2(k)I2 - W 2 ( k l 2 I

(4.1) (4.4

and, comparing imaginary parts, for small y

rdk) = fsir

using (2.39) and (2.34). In fact, if some damping 'ys is introduced into the equation (2.15) for G and into the corresponding equation for H while yp is introduced into the phonon equations, the denominator becomes
((U

- Zys)'- (1 + < 2 ~ ) W O z ] { ( W

- iyp)2- W b 2 } - < 2 u w o 2 W k 2

(4.3) (4.4)

and the widths of the coupled modes, again for small y , are

ra(k) = fS'YS +fplYP

using (2.39). Comparing (4.2) r appears like a spin damping. I t is interesting to compare I with the direct spin relaxation of isolated impurity spins. ' I n the low-temperature region the form in our notation (Scott and Jefferies 1962) is (4.5)
y t is only appreciable for w
N

w0

and, using

go

tanh(@wo), this may be written

Po =

1(--)

3.rra2w0

WO

cosech(/3wo).

T h e main difference between (4.6) and (4.5) is near 7' = 0 as is demonstrated in figure 2. T h e ordinary direct process gives a constant width in this limit while Po --f 0 since the main effect of the spin-phonon interaction is to produce coupled but undamped modes. T h e scattering is coherent; when a magnetic atom relaxes the emitted phonon excites its

1033 neighbour and the disturbance propagates through the lattice undiminished. The final term in (4.6) may be written

Spzn-phonon effects in thermal conductivity

a-

(SE showing that it is essentially proportional to the fluctuations in (S,). r N W = &rc2K,T(~0/~,)3.

>

(4.7)
At high T,

14

O 0

04
X

08

I2

Figure 2 . Comparison of width of coupled mode with inverse relaxation time of &lute salt. Curve h is a plot of y = &(cotht x - tanh Bx); curve B is a plot of y = & coth ax.

T h e expression (2.34) for is unsatisfactory at small w < W, and small T in that it becomes negative. However, I? itself is very small in this region and these low-w modes contribute only a very small effect to the thermal conductivity considered later. This failure of the theory is therefore unimportant for the considerations of this paper and we have not attempted to improve the theory to remove this unsatisfactory feature. Equation (2.25) may be used to describe a dilute crystal where a fraction c of all sites are occupied at random. Only occupied sites are included in the equation. If we redefine (2.18) as 1 (4'8) G(k, W ) = - G d w ) expbk . (Ri- R d

c-v2'
13

also to include only occupied sites, the equation for G(k) remains unchanged except for a factor c multiplying R(k) in (2.28). This simple expression arises because Rif = 0 and so the in (2.25)is replaced by cXc,,, when we average over configurations. The result is equivalent to changing U to cu in determining the new dispersion relation from (2.35) and the new damping from (2.34). As c decreases the modes are seriously modified over a narrower range and the damping increases. For small c, I = W, the result for isolated ' atoms.

4.2. Magnetic interactions In any concentrated paramagnetic salt there will be interactions between the magnetic ions due to dipole-dipole forces and possibly to exchange forces as well. If these are large they will lead to magnetic ordering. We are interested in the case when such interactions are less than kw,. If our ions are of the Kramers type this means that any low-temperature ordering is destroyed by the applied magnetic field and an effective

1034

R. J. Elliott and J. B. Parkitzson

ferromagnetic order superimposed. The general form of these interactions is

c z:D,I"R&-fS,o
04
I1

(4.9)

where M , ,B represent the three Cartesian directions. This in turn may be written in terms of the a , operators using (2.6). Some of the terms will be quadratic in a. These should properly be included in (2.10); the spatial dependence of D,, \vi11 lead to a dispersion in the magnetic excitation. T h e theory of the previous sections nil1 go through with replaced by w,(k). The coupled modes will not be much altered near the cross-over but the lowfrequency mode i d not be flat and will have the form of wo(k) at larger k. The terms in S,,S,, are partly quartic in n. These can be approximately included by replacing this by $u(S,;+ SI..) and leads to an effective temperature dependence in w,(k). In the Kraniers case this corresponds to a shift in the spin excitation energy due to the demagnetizing field. The fluctuations in S,,S,z, and terms like S,,S,, which are cubic in a, lead to a damping of the modes. Since it depends entirely on the spin part we shall assume that it contributes to the width of the coupled modes like ys in (4.4). For isolated spins it has been shown that the dipole-dipole width varies like the fluctuation as the spin system orders (Kanibe and Isui 1952, Syare and Seidel 1964)
ys = Yd( ( ; 8

) - (Sz

(4.10)

and tends to zero as T +- 0. Here Yd K CctirC,(Di,a4)2. It is also possible to carry out perturbation theory at T = 0 with the terms cubic in a among the coupled modes. The process is small, though not esactly zero. For example the k = 0, w = w o mode can decay into two modes of t k and w = )wo. These modes are, which is negligible. however, largely phonon-like and ys
N

4.3. Anharmonic effects The purely phonon part of the Hamiltonian involves terms of order higher than quadratic in the displacements. These lead to terms cubic, quartic, etc., in the c operators. The cubic terms give a damping of the phonon part of a mode by allowing it to split into two other phonons, However, these normal processes conserve the overall k value and do not contribute to the thermal resistance. Other effects become important at high 2 ' . The theory of these effects has been extensively studied (Klemens 1958) and will not be discussed further, Any purely phonon damping will be assumed to contribute to the coupled modes like yp in (4.4). 4.4. Rnman processes There will also be terms in the Hamiltonian cubic in the operators of mixed U and C. Those linear in n and quadratic in c give rise to the so-called Ramaii processes in magnetic relaxation (Van Vleck 1940, Orbach 1961). For a Hamiltonian of the form
kk'

1 2 2 - -12H 2 ~ k ~ l c , ) 1 2 ( a l C a l t e x p ( i ( k + k ) ( )
2
I

RI)(Ck+C-k+)(Ck,+C-k'+)

(4*11)

'i \

the spin relaxation rate is found to be of order (977)6!~,~(h,T)~ Ys = ( Aw , ) ~ ~ A * For Kramers ions c p x hw,, and in that case a higher-order process giving
Ys =

(4.12)

9?7c2(kB ) T' 7!AA2(Aw,)6

dominates, where A is the separation to some excited state, Thus at low T this process leads to a very small width. In fact it does not go entirely to zero. For example the k = 0 mode may decay into two phonons of 5 k and w = i w 0 . This rate is ys = 3m22(hwo)4/16(~%)3 in the non-Kramers case, and 3 n ~ 2 2 ( A ~ o ) 6 / 1 6 A 2 ( ~ ~ the Kraniers case. in , ) 3

Spin-phonon effects zn thermal conductivzty

1035

T h e lk" process also gives a damping yp to the phonon modes. This is approximately
7 6 2 ' w k 2 ( wk2

YII =

+w2)

160,~

(4.13)

for the process where the phonon with k interacts with another at k+k' and a spin excitation of k'. There is also a scattering of the phonons 08 the spin fluctuations, though at terms like (4.11) containing S,, rather than This will have a form similar to (4.13) but containing ((S,2> (S,)'). 4.5. Other spin-phonon interaction T h e interaction (2.3) gives effects similar to those described in $4.3 above. It is in fact the only cubic term which has not yet been considered, being linear in the c operators and quadratic in U . I n the uncoupled system it gives essentially zero effect. The destruction of a spin excitation must be accompanied by the creation of another and the creation or destruction of a phonon. T h e destruction of a phonon must be accompanied by the simultaneous creation and destruction of a spin. But all the spin excitations have the same energy and so energy conservation is impossible. In the coupled system the mixing of the modes and the modification of the dispersion curves allows the processes to take place but the probability is extremely small. For example the k = 0, w = w o spin excitation can decay into two & k, w = +w0 using the smaIl spin part of one of these. A phonon k with wk can decay into one of w i c - w o using its small spin part and creating a spin excitation near w 0 . Both processes will go much better using the Raman term of $4.4 which did not depend on the small mixing. We have in fact estimated these processes in detail using an extension of the Green function method. YEsL' is added to 2i and the higher-order terms found in the equation i of motion are decoupled as in $ 2. G(k, w ) is found in the form (4.10) with a denominator

(4.14) This confirms that both ys and yp are small over the whole range and may be neglected. This is in agreement with the conclusion of Mills (1965) who studied the strongly mixed modes in the classical limit. 4.6. Imperfections All the interactions treated so far have been consistent with complete periodic symmetry in the lattice, But any real crystal will contain imperfections. The boundaries of the specinien cause all the excitations to have a mean free path, h say. The composite modes will therefore have a damping Yt(k) = +)/h (4.15) where the velocity is given by (2.29). Impurity scattering of the phonons is usually taken to give a damping of the Rayleigh type (cf. Klemens 1958) yp(k) = bwk4. (4.16) In the comoosite modes we shall assume a width of this kind proportional to the phonon content a i [n (4.4). Random local strains give rise to a spread in the characteristic w o which will be Gaussian in form. This may be expected to be much larger in the non-Kramers case since electric fields may then directly affect the splitting. We shall assume this to give a constant ys which will give a damping in the coupled mode proportional to the spin contribution (cf. (4.4)).

1036

R. J. Elliott

oiid

J. B. Paifkinson

5. Paramagnetic relaxation?
Magnetic resonance or other optical excitation experiments in this system would be concerned with the k = 0 mode at w = w o . Relaxation measurements would measure the damping of this mode. Kormally this is doiiiinated by the direct spin-phonon process given by (4.5). Our theory gives a very much longer relaxation time at low T given by (4.6). This can only be observed if there are not other damping mechanisms in this region, The remnant of the Raman process was shown to tend to a constant as T -+ 0 which could be obtained by extrapolating from the high T results. Spin-spin relaxation would also be difficult to disentangle. The major effect would be the dipole-dipole contribution and this, comparing (4.10) with (4.7),will have a similar variation at low T. Crystals with large spacing between the magnetic ions would be essential to avoid the dominance of this effect. The effect described in $4.5 is negligible and the local imperfections of 4.6 do not give an actual damping.

6. Thermal conductivity The main object of this work is to describe the thermal conductivity given by our model of a spin-phonon system. This is given by expression (3.1). We use (3.3) to give the velocity of the coupled modes and derive the specific heat by differentiating (3.10) including the variation of U. T h e main difficulty in comparing with experiment lies in choosing appropriate damping constants y for the various processes discussed in $$4 and 5. An ideal crystal may be thought of as one with only boundary scattering (4.15).Adding the intrinsic width (4.11) gives

I n figure 3 we plot the ratio of K,, the thermal conductivity in the presence of spin-phonon coupling, to KO, due to the unperturbed phonons. I n our model two phonon branches that remain unchanged so that the actual conductivity is 2K,+K,. Curve A gives the full result using (7.1). Curve B represents the result with r = 0, although the modifications

20
fiU,/k,

40
(OK)

60

Figure 3 . Thermal conductivity of an ideal non-Kramers crystal. Curve A includes intrinsic width; curve B is due to modification of velocity and specific heats of coupled modes only

t We are particularly indebted to Professor P Wagner for many discussions of this aspect Of the problem. He has made a detailed feasibility study of possible experiments to show the effects discussed here.

Sptn-phonon effects zn thermal conductivity

1037

of S,(k) and are included. We see that both effects are of similar magnitude. The Curves in figure 3 are plotted at fixed T = 1 OK and variable w 0 in a non-Kramers salt. Since E depends on W O in different ways for Kramers and non-Kramers salts a somewhat different curve is obtained for the Kramers case as shown in figure 4. In each case the Debye temperature hw,/kB was taken as 60 OK, v the velocity of sound as 2 x lo5cm sec-l / 0.01 and X = 1 cm. For the non-Kramers case t l ~ , ~ ~= k , OK and in the Kramers case KB2/hcoO 9 x = OK-'. T h e former corresponds roughly to the value of spin-lattice coupling for Ce in lanthanum ethyl sulphate as measured by Scott and Jefferies (1962) where the two levels are the low-lying crystal-field levels 4 ~ ~= /5.7 OK.~ Strictly speaking k

0 96-

. k k 0 880 84. 0 80.

0 92-

Figure 4. Thermal conductivity of an ideal Kramers crystal. Curve A is including intrinsic width; curve B is due to modification of dispersion relation and specific heats of coupled modes only.

t
0 47

k.
0

k-

0
0

Figure 5. (a) Theoretical thermal conductivity of a non-Kramers crystal with static strains as a function of level splitting a t various temperatures. (b) Same as (a) with the inclusion of some impurity scattermg of the phonon part of the coupled modes.

1038

R. J. Elliott and J. B Parkznson

both levels are Kramers doublets. The coupling in figure 4 was arbitrarily chosen to give an effect of the same magnitude-normally the coupling may be expected to be smaller in the Kramers case. I n real crystals other mechanisms are likely to be more important than the intrinsic width in scattering the spin part of the modes. Dipole-dipole in the Kramers case and random strains in the non-Kramers case seem likely to be the most important. We have made detailed calculations with (4.4) in the latter case with ys constant and yo given by (4.16). I n this calculation w o was replaced by (~oz+ysa)liz take account of the finite to splitting in zero field. Typical curves are given in figure 5 for large hys/kB = 3 OK, A = 1cm including impurity scattering with b = 1.02 x lo- sec4 OK and without it ( b = 0). The values of E, 21,and w, are those used for figure 3. These may be compared with the results of Mcclintock (1966), on praseodymium ethyl sulphate which are shown in figure 6 after
14

0 0
I

Figure 6. Results of McClintock (1966) on praeseodymium ethyl sulphate after smoothing to eliminate some impurity effects,

I
,, 0
v

20

40

60

k 0 . k 0 04

Figure 7. (a) Theoretical thermal conductivity of a Kramers crystal with dipoledipole interactions as a function of level splitting at various temperatures. (b) Same as (a)with the inclusion of some impurity scattering of the phonon part of the coupled modes.

Spin-phonon eflects zn thermal conductivity

1039

smoothing to eliminate some oscillations whose origin is obscure. Unfortunately direct comparison is not possible since the several parameters in the theory have not been obtained independently in this case. The agreement in the general shape of the curves is encouraging. The most detailed studies have been made on holmium ethyl sulphate (McClintock et al. 1967) but here the presence of three levels makes the theory too difficult. One concentrated Kramers salt has been measured in some detail: lanthanum cobalt nitrate by Berman et al. (1963). Unfortunately measurements were not made with kwo >> K,T and these are necessary in order to separate out dipole-dipole effects. Further measurements on this type of material would be most useful. Typical curves for such a material with Ayd/KB = 3 OK are shown in figure 7. The other parameters are the same as in figure 5 . As in that case w o is replaced by (uoz+y,2)12. In this case ys depends on U and has to be determined self-consistently. The general shape of our theoretical curves is reminiscent of those of Orbach (1962) and Huber (1964). They do, however, differ in magnitude and in detailed shape. We believe with Muller and Tucker (1966) that it is more satisfactory to include the major part of the direct spin-phonon coupling by generating coupled modes. It would be extremely interesting to observe the form of the intrinsic width by relaxation or conductivity experiments, but the interference of other effects make this appear a difficult task,

Acknowledgments We are indebted to Professor P. Wagner, Dr. H. Rosenberg, Dr. D. Walton and Mr. P. McClintock for many interesting discussions. This work was supported by a grant from the United Kingdom Atomic Energy Authority.
References
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