Mat. Res. Bull. Vol. 8, p p . 195-Z00, 1973. Pergamon Press, Inc.

Printed
in t h e U n i t e d S t a t e s .

DEBYE-WALLEI{ FACTOh' A N D 1)EBYE TEMPERATURE FOR

Fe, Mo, Ta, AND W

M.Merisalo a n d T. P a a k k a r i
Department of P h y s i c s , University of" H e l s i n k i
Siltavuorenpenger 20 c, S F - O O ] 7 0 l l e l s i n k i 17
Finland

(Received December 4, 197Z; Refereed)

ABSTRACT
Tile D e b y e - W a l l e r parameter and the Debye temperature
for iron, molybdenum, tantalum, and tungsten have been
calculated from general force constant models. Compal-
ison of the x-ray Debye temperatures wit]] t h e h e a t
capacity Debye temperatures is m a d e a n d d i s c u s s e d .

Introduction

A ~[reat deal of interest is attached to a comparison of

values for the Debye-Waller parameter and the Debye tempera-
tures obtained from x-rays with those resulting from calcula-
tion from a detailed description of tile p h o n o n states by a
force-constant model (I). Where experimental determinations of
these quantities are not available, the values calculated from
a reliable theoretical model can be used as the best estimates
in diffraction experiments. On the other hand, where accurate
experimental determinations have been made, a comparison with
the calculated values provides a test of the phonon character-
istics, and thus of the models used.

In the present paper the values of" t h e Debye-Waller par-

ameter and the Debye temperature for iron, molybdenum, tanta-
lum, and tungsten have been calculated from general force

195
196 DEBYE-WALLER FACTOR; DEBYE TEMPERATURE Vol. 8, No. Z

constant models determined recently from inelastic neutron

scattering experiments (2-7). Comparison of the x-ray Debye
temperatures with the h e a t capacity Debye temperatures is
also made and discussed.

Calculations

The results of inelastic neutron scattering measurements

are usually interpreted in terms of the interatomic force-
constants of the Born - yon Karman theory of lattice vibrations
(8). Using the force-constants given by various authors, the
phonon eigenfrequencies and eigenvectors were computed for
1000 evenly distributed points in the Brillouin zone [details
of this calculation are presented in Ref.(9)]. This frequency
spectrum was then applied in calculating the Debye-Waller
parameter

8fl 2 ~ E
B- 3raN L ( ~ ) q J '

and the specific heat

Cv : W L '
qJ

where E is the energy of the (qj)-mode, m is the m a s s of the

atoms in the crystal. The corresponding values of the D e B y e
temperatures derived from diffraction measurements (~M) and
from specific heats (el)) w e r e obtained using Debye's theory.
The contribution from q = 0 in the sums was calculated in the
conventional way by integrating over a sphere of v o l u m e equal
to one thousandth of that of the Brillouin zone around the
origin and by assuming that the freguency in this region is
given by the average velocity times the w a v e vector. No sig-
nificant improvement could be found when a denser mesh of
the w a v e vectors was used.

The results are given in T a b l e I.

Volo 8, No. g DEBYE-WALLER FACTOR; DEBYE TEMPERATURE 197

TABLE 1

V a l u e s of D e b y e - W a l l e r P a r a m e t e r B (~2), D e b y e
T e m p e r a t u r e s ~M a n d ~D (K), a n d the R e l a t i v e
Difference ~=~/~': I (~) at T : 296 K. V a l u e s
of ~M' h a v e b e e n c a l c u l a t e d b y the a p p r o x i m a -
t i o n of Z e n e r a n d B i l i n s k y .

Element B eM eD GM ,

I 0. Z41 495 418 ~28 1.6 Force constant model

from Re#.(2)
((gM: 435 f r o m R e f . 9)
Fe 0.333 440 416 ~26 3.3 Force constant model
from ~{ef. (~)
0.~0 4~9 424 4~5 1.8 Force constant model
from Ref.(~)
[ 0.~86&0.016 409~9 Experimental value
at 298 K from Ref.(12)
Mo 0.279 ~99 ~61 371 7.6 Force constant model
f r o m Ref. (5)
Ta ().~99 238 229 229 ~.9 Force constant model
from R~f.(6)
# 0 ° 159
I
~6 910 ~18 9.1 Force constant model
from Rer.(7)
W < 0.]89±0.008 ~25±7 Experimental value
at ~00 K from Ref. (14)
\ 0.]~6±0.012 ~77±11 Experimental value
from Ref.(15)

Discussion

It w a s first pointed out b y Zener and Bilinsky (10) that

the D e b y e temperatures % 1 and ~) are not defined identically.
Their approximate approach in w h i c h the D e b y e model is u s e d
to take care of d i f f e r e n t avera{~es ~ i v e s eM/~ as a f u n c t i o n
of P o i s s o n ' s ratio and leads to the conclusion that G M should
always exceed ~ by p e r h a p s a few p e r cent (cf. Ref. 11, p.
220). Since then this conversion has been used by m a n y
authors in o r d e r to c o m p a r e the v a l u e s of ~ o b t a i n e d in terms
of % From different methods (of. |~efs. 12 and I~), or to
obtain a motion parameter for a crystal model when a reliable
diffraction measurement is not available.

The results in T a b l e I indicate that the v a l u e s calcu-

198 DEBYE-WALLER FACTOR; DEBYE TEMPERATURE Vol. 8, No. Z

lated by the approximation of Zener and Bilinsky (~') are

systematically smaller than fhose calculated from a real
Frequency spectrum (GM). Particularly in the case of Mo and
W the conversion is rather unsuccesful and may lead to mis-
leading results when applied, for example, to correct x-ray
intensity measurement for temperature effects.

For Fe there were three independent sets of force-con-

stants available. The range ± 4 K of the calculated values
indicates fairly good agreement between various models.

Experimental determination of the Debye-Waller parameter

B has been made only For Fe (12) and for W (14,15). A compar-
ison in Table 1 shows that the x-ray result for Fe is some-
what larger than the calculated result. Unfortunately, the
accuracy of the experimental x-ray values seems to be rather
low, which is demonstrated by the contradictory results for
W. On the other hand, it should be kept in mind that all the
calculations have been made in the harmonic approximation.
To estimate the effects of this approximation more accurate
x-ray determinations of the Debye-Waller parameters are
needed.

References

I. B.T.M. Willis, Acta Cryst. A25, 277 (1969).

2. V.J. Minkiewicz, G. Shirane and R. Nathans, Phys. Rev.
162, 528 (1967).

J. B.N. Brockhouse, H.E. Abou-Helal and E.D. Hallman, Solid

State Comm. ~, 211 (1967).
4. J. Bergsma, C. Van Dijk and D. Tocchetti, Phys. Letters
24A, 270 (1967).

5. C.B. Walker and P.A. Egelstaff, Phys. Rev. 177, 1111 (1969).

6. A.D.B. Woods, Phys. Rev. 136 , A781 (1964).

7. S.H. Chert a n d B . N . Brockhouse, Solid State Comm. ~ , 73

(1964).

8. M. Born and K. Huang, Dynamical Theory of Crystal Lat-

tices. Clarendon Press, Oxford (1954).
Vol. 8, No. Z DEBYE-WALLER FACTOR; DEBYE TEMPERATURE 199

9. T. Paakkari and M. Merisalo, Ann. Acad. Sci. Ferm. ~ VI,

No 350 ( 1 9 7 0 ) .
10. (3. Zener and S. Bilinsky, Phys. Rev. 50, 101 (1936).

11. R.W. James~ The O p t i c a l P r i n c i p l e s of the D i f f r a c t i o n

of X-rays. Bell and Sons, L o n d o n (1962), page 220.

12. F.H. Herbstein and J. Smuts, Phil. Mag. ~, 367 (1963).

I 3 . R.H. Wilson~ E.F. Skelton and J.L. Katz, Acta Cryst. 21,
635 (1966).
14. T. P a a k k a r i and P. Suortti, plhys, star. sol. 28, 3~9

15. L.K. W a l f o r d 9 Mat. Res. Bull. ~ 137 (1969).