Normalization of Diffraction Data from Liquids

Aneesur Rahman

Citation: J. Chem. Phys. 42, 3540 (1965); doi: 10.1063/1.1695757
View online: http://dx.doi.org/10.1063/1.1695757
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THE JOURNAL OF CHEMICAL PHYSICS VOLUME U, NUMBER 10 15 MAY 1965
Normalization of Diffraction Data from Liquids
ANEESUR RAHMAN
Argonne National Laboratory, Argonne, Illinois
(Received 9 November 1964)
In any system, the effective exclusion of an atom from the immediate neighborhood of another atom
can be used to derive a necessary (but not sufficient) condition which the diffraction pattern of the system
has to satisfy. This condition provides a new method of scaling the observed diffraction data from liquids.
The currently available x-ray and neutron-diffraction data on liquid argon at 84K are found to differ in a
systematic manner, and this discrepancy appears to be beyond the experimental uncertainties of the data.
It is demonstrated that the above-mentioned condition can be used as a reliability criterion as well. Using
this criterion, it is found that the neutron-diffraction data are much more reliable.
I
N this paper we derive a condition that the dif-
fraction pattern of a liquid has to satisfy. The
search for such a condition was motivated by the fact
that diffraction data for the same liquid obtained in
different laboratories seem to differ in a systematic
manner. We first exhibit that this condition can be
used as a check on the reliability of experimental
diffraction data on liquids. The possibility of using
this condition as a means of normalizing the observed
data is mentioned briefly at the end.
Since we are concerned with the case of liquids alone,
we take the pair distribution function g(r) to be
isotropic; we can thus write g(r) as a function of the
magnitude of r.
Normalizing the function g(r) so as to make it unity
at large 1', we have
(1)
where n is the number density, K= I K I =411' sin8/X for
a beam of wavelength X scattered through angle 28,
l+Y(K) is the diffracted intensity arising out of the
atomic distribution.
Equation (1) is the familiar equation which, after
angle integrations are performed, becomes
41rnr2[g(r) -lJ = "'Y(K) sin(Kr) dK. (1')
The existence of a violent repulsion between atoms
when they come close enough implies that, at moderate
temperatures, the function g(r) is effectively zero for
any r<re, where re is a fairly well-defined hard-core
diameter of each atom. [In argon at 84 OK, re is about
3.05 A, and it is quite safe to say that for 1'<3.0 A
say, g(r) in liquid argon is certainly zero, for all
practical purposes. ]
Thus, for O:$r:$re, we have from Eq. (1')
sin(Kr)dK. (2)
Multiplying both sides of Eq. (2) by exp( -illr)
and integrating over r in a sphere of radius L, we get

X {jo[(K+IL) LJ-jO[(K-IL) LJ}, (3)
where IL is arbitrary and L has any value such that
L<re;jo andjl are spherical Bessel functions.
We now demonstrate that Eq. (3) can be used as a
reliability criterion for experimental diffraction data
on liquids. For this purpose, we use the experimental
data for diffraction from liquid argon at 84K obtained
by x rays and by neutrons. First we briefly mention
the normalization procedure in each of these cases.
In the case of x rays, if I(K) is the scattered intensity
after being corrected for incoherent scattering, then
is related to I(K) by the equation
(4)
where f is the atomic scattering factor and N is a
normalization constant.
In the case of neutrons, the scattered intensity I(K)
is given by
I(IC) =I
oo
{l+( (a)2/ (a
2
)h(K)), (5)
where loo is again a normalization constant, (a
2
) - (a )2
is the incoherent scattering cross section, and (a)2
the coherent scattering cross section.
To use Eq. (4) to obtain one requires an ac-
curate value of the incoherently scattered x-ray in-
tensity and of f(K) throughout the range of K covered
by the experiment. Assuming that this has been done,
we denote the obtained from Eq. (4) by
The use of Eq. (5) to get depends on an extra-
polation of the intensity to K=O. Then, knowing that
.6T being the isothermal com-
pressibility at temperature T, one can get (a)2/ (a
2
)
and hence Assuming that this has been done,
we denote the obtained from Eq. (5) by
Now let us compare the and for liquid
argon at 84K. The latest experiments in this context
are those of Gingrich and Tompson
l
for x rays and
* Based on work performed under the auspices of the U.S. 1 N. S. Gingrich and C. W. Tompson, J. Chern. Phys. 36, 2398
Atomic Energy Commission. (1962).
3540
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A NEE SUR R A H MAN 3541
3.0 I + r (Ie)
FIG. 1. The experimental curves
for 'Y(K) obtained with x rays and
with neutrons.
2.5
2.0
I.S
1.0
0.5
from X-roy doto'
from Neutron dota
2

"-(4,, sinBIA) IN a-I
of Henshaw
2
for neutrons. These are illustrated in
Fig. 1,3 From this figure, one concludes that there is a
systematic error in one relative to the other.
The utility of Eq. (3) as a check on the experimental
1.5
-- S(L,p)
o 0 0 0 Sx(L, pI
1.0 c c c c SN(L,pl
0.5
-2
-4
-6
-8
o
FOR L 3.0-1
NOTE FACTOR OF TEN
IN SCAL.E ABOVE AND
BELOW ZERO OF ORDINATE
o
0.5 1.0 1.5
P IN 1-
1
a
o
2.0 215
'Y(K) is now shown. Let us denote the number on the
left side of Eq. (3) by S(L, p,). Let us denote by
Sx(L, p,) the integral on the right side when 'YX(K)
is used to evaluate the integral and by SN(L, p,)
when 'YN(K) is used for that purpose.
Figure 2 shows the plot of Sx(L, p,), SN(L, p,)
and of S(L, p,) for L=3.0 A. The manner of choosing
the scale for the ordinate is simply to bring out the
slight degree by which SN(L, p,) differs from S(L, p,).
It is immediately obvious from Fig. 2 that for L = 3.0 A,
'YN(K) satisfies Eq. (3) and 'YX(K) does not.
However, Fig. 3 shows the values for L= 1.0 A.
Note that Sx(L, p,) is wrong in sign, as well as in its
slope with respect to p,. The discrepancy in SN(L, p,)
is now a little more apparent than in Fig. 2, showing
that as L gets smaller the demands on the accuracy
of 'Y(K) for satisfying Eq. (3) become more exacting.
The reason for this rather unexpected result, con-
cerning the reliability of 'YX(K), is most probably re-
lated to the large-angle fitting procedure. A small
error in f(K) at large K (and f is not so accurately
1.0
0 0
0
0.5
o
--
SIL.I')
o 0 0 0
S.IL. p)
D D 0 0 S.IL. p)
FOR L'.O/'
FIG. 2. Comparison of Sx(L, /-I) and of SN(L, /-I):with S(L, /-I) 0
for L=3.0 A. The discontinuity at /-1= 1.5 A -1 is due to the choice
of a different scale for the ordinate above and below the dashed
0
0
0
line. 0
I D. G. Henshaw, Phys. Rev. 105, 976 (1957). 0 0.5 1.0 I.'
2.0 2.' 3.0
I'
IN
.-1 3 The x-ray curve was drawn with a tabulated set of experi-
mental values of l+'Y(K), kindly furnished by Gingrich and
Tompson. The neutron'curve was drawn from an enlargement of FIG. 3. Comparison of Sx(L, /-I) and of SN(L, /-I) with S(L, /-I)
the figure in Ref. 2. - for L= 1.0 A.
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3542 DIFFRACTION DATA FROM LIQUIDS
known at large K) can propagate throughout the whole
range of angles through the normalization constant
N of Eq. (4). The fitting procedure is also very sensitive
to the value used for the incoherent scattering at large
angles.
This conjecture regarding the possible reasons for
the failure of 'YX(K) to satisfy Eq. (3) naturally leads
us to suggest Eq. (3) as a means of normalizing experi-
mental data.
In the case of x rays, one would write
(6)
where N would be determined not by fitting at large
angles but by substituting the above function into
Eq. (3). In doing this, one would be using two favorable
facts: first, the incoherent scattering is only a minor
THE JOURNAL OF CHEMICAL PHYSICS
part of the total in regions of K which determine the
value of the integral on the right of Eq. (3); and
second, f(K) is relatively more accurately known in
this region of K than in the region of large K.
In the case of neutrons, one would write
and, by substituting into Eq. (3), one would try to
improve upon the experimental uncertainties inherent
in extrapolating to large angles to get 100 and to small
angles to get (a)2j (a
2
).
ACKNOWLEDGMENT
The author is indebted to Lester Guttman for many
helpful discussions.
VOLUME 42, NUMBER 10 15 MAY 1965
Electron Spin Resonances in Gamma-Ray Irradiated Sodium Chlorate. I
F. T. GAMBLE
Denison University, Granville, Ohio and Battelle Memorial Institute, Columbus, Ohio
(Received 18 November 1964)
Single crystals of NaCIO
a
were subjected to gamma-ray irradiation at room temperature. Analysis of
the resulting electron spin resonance spectrum indicates the production of three paramagnetic centers,
initially, each with an effective spin of l. The measured parameters of a center having resolved hyperfine
structure and identified as CI03 were gn =2.00850.00l0, g.L= 2.00900.OOlO, A = 14.80.1 G, and
B=21.20.1 G. No hyperfine interaction was detected for the remaining two centers having gO =2.007
0.001 and g.L=2.0200.001, and g ~ 2 . 0 0 8 respectively. The centers are reasonably stable at room tem-
perature for several months.
INTRODUCTION
D
EFECT structures are produced in single crystals
of a number of materials with exposure to ionizing
radiation. Where paramagnetic centers are created,
these defects may be studied by electron spin resonance
(ESR). Information gained from these studies is useful
in the analysis of the electronic energy states of the
various atoms and molecules of the crystals and con-
tribute to our understanding of the crystalline fields
which exist in these solids. In addition, it may be used
to identify the breakdown mechanism in the crystal
structure as the irradiation continues. The present
paper reports on the initial paramagnetic centers which
are produced when single crystals of sodium chlorate
are irradiated with gamma rays.
EXPERIMENTAL DETAILS
Single crystals of sodium chlorate were grown by
slow evaporation from aqueous solutions of reagent-
grade powders. Samples were maintained in dry atmos-
pheres at room temperature except during irradiation
and during ESR runs. ESR background studies indi-
cated that no detectable numbers of paramagnetic
centers were present prior to irradiation.
Gamma-ray irradiations were performed at room
temperature in calibrated tubular 6OCO sources at the
Battelle Memorial Institute. ESR observations were
made at room temperature with a conventional X-band
spectrometer. Sample mountings permitted rotation
of the crystals about a variety of internal axes relative
to the external magnetic field.
Sodium chlorate crystallizes in the cubic tetrahedral
class and has been assigned to the T4(P2
1
3) space
group.! The unit cell consists of four molecules in a
slightly distorted NaCl structure. The bonding between
the sodium and the chlorate group is predominantly
ionic.
2
The chlorate ion consists of three oxygen atoms
arranged in an equilateral triangle about a chlorine
atom to form a fiat pyramid.
3
The axis of each chlorate
1 R. W. G. Wyckoff, Crystal Structures (Interscience Pub-
lishers, Inc., New York, 1948), Vol. II.
2 R. Bersohn, J. Chern. Phys. 29, 326 (1958).
3 C. Aravindakshan, Z. Krist. Ill, 241 (1959).
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