Polarized Crystal Spectra of CoF2 and Co0.06Zn0.

94F2
Lois Jacobs Zimring and J. W. Stout

Citation: The Journal of Chemical Physics 51, 4197 (1969); doi: 10.1063/1.1671779
View online: http://dx.doi.org/10.1063/1.1671779
View Table of Contents: http://aip.scitation.org/toc/jcp/51/10
Published by the American Institute of Physics
 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 51, NUMBER 10 15 NOVEMBER 1969

Polarized Crystal Spectra of CoF 2 and COO.06ZnO.94F2*

LOIS JACOBS ZIMRINGt AND J. W. STOUT
Department of Chemistry and James Franck Institute, University of Chicago, Chicago, Illinois 60637
(Received 16 August 1968)

Polarized spectra of oriented single-crystal CoF, and COO.06ZnO.94F, are presented in the range 5000-
25000 em-I at 298, 77, and 20.4°K. Molar extinction coefficients and oscillator strengths are calculated.
The spectra of CoF, and of dilute COH in ZnF, are very similar. The principal bands are identified as transi-
tions from the 4Tlq(4F) ground level to 4T,.(4F), 4A,.(4F) , and 4TI .(4P) levels. A value of Dq=715 cm-1
is obtained. A sharp electric dipole line, 10 crn-I wide, is seen at 22 768 cm-1 in CoF, at 20.4°K.

CoF2 is one of the transition-metal difiuorides of the
rutile structure1 which are simple examples of two
sublattice antiferromagnets. Below the Neel tempera-
ture of 37.700 K,2 CoF2 is magnetically ordered with
spins aligned parallel and antiparallel to the tetragonal
axis. Numerous investigations3-11 have been made of
the magnetic properties of CoF2 • The positions of the
electronic levels of Co2+ in a CoF2 crystal may be deter-
mined from spectroscopic measurements, and with
sufficient understanding of the electronic states the
magnetic properties may be calculated. Since the work
described in this paper was begun, several reports
describing features of the near-infrared, visible, and
ultraviolet spectrum of COF 212-19 and its solutions in
* Supported by the National Science Foundation and by the
U.S. Office of Naval Research. We have benefited from facilities
provided by the Advanced Research Project Agency for materials
research at the University of Chicago.
t Present address: Department of Natural Science, Michigan
State University, East Lansing, Mich.
I J. W. Stout and S. A. Reed, J. Am. Chern. Soc. 76, 5279
(1954) .
'E. Catalano and J. W. Stout, J. Chern. Phys. 23,1803 (1955).
3 J. W. Stout and L. M. Matarrese, Rev. Mod. Phys. 25, 385
(1953) .
4T. Nagamiya, K. Yosida, and R. Kubo, Phil. Mag. Supp!. 4,
1 (1955).
5 M. Tinkham, Proc. Roy. Soc. (London) A236, 549 (1956).
6 H. M. Gladney, Phys. Rev. 143, 198 (1966).
7 M. E. Lines, Phys. Rev. 137, A982 (1965).
8 V. Jaccarino, R. G. Shulman, and J. W. Stout, Phys. Rev.
106,602 (1957).
9 P. L. Richards, J. App!. Phys. 35, 850 (1964).
10 D. N. Astrov, A. S. Borovik-Romanov, and M. P. Orlova,
Zh. Eksp. Teor. Fiz. 33,812 (1957) [SOy. Phys.-JETP 6,626
(1958) ].
11 R. A. Cowley, P. Martel, and R. W. H. Stevenson, Phys.
Rev. Letters 18, 162 (1967).
12 R. Pappalardo, Spectrochim. Acta 19, 2093 (1963).
13 A. Ludi and W. Feitknecht, Helv. Chim. Acta 46, 2226
(1963) .
14 V. V. Eremenko and A. I. Zvyagin, Fiz. Tverd. Tela 6, 1013
(1964) [SOy. Phys.-Solid State 6, 782 (1964)].
15 V. V. Eremenko and A. I. Belyaeva, Fiz. Tverd. Tela 6,3646
(1964) [SOy. Phys.-SoJid State 6, 2918 (1965)].
16 A. I. Zvyagin and V. V. Eremenko, Ukr. Fiz. Zh. 10, 525
(1965).
17 P. G. Russell, D. S. McClure, and J. W. Stout, Phys. Rev.
Letters 16, 176 (1966).
18 D. S. McClure, R. Meltzer, S. A. Reed, P. Russell, and J. W.
Stout, in Optical Properties of Ions in Crystals, H. M. Crosswhite
and H. W. Moos, Eds. (Interscience Publishers, Inc., New York,
1967), p. 257.
19 J. P. van der Ziel and H. J. Guggenheim, Phys. Rev. 166,479
(1968).
4197
MnF220.2I have appeared, but there is no quantitative
information on molar extinction coefficients and only
rough estimates of oscillator strengths have been ob-
tained. In the present paper we report, for the range of
5000-25000 cm-I, polarized crystal spectra of CoF2 and
COO.06ZnO.94F2, at temperatures of 20.4, 77, and 298°K.
The molar extinction coefficients are plotted as a func-
tion of wavenumber, and integrated oscillator strengths
are tabulated.
EXPERIMENTAL
Crystal Samples
Powdered ZnF2 and CoF 2, dried in an atmosphere of
HF at 800°C, were prepared as described previously.2.22
In order to avoid the Ni impurity commonly present in
commercial cobaltous salts, the CoF2 was made from
sodium cobaltinitrite. Single crystals of COO.06ZnO.94F 2
and ZnF2 were grown in thin-walled graphite crucibles,
in the apparatus used23 for MnF 2. The center of the
furnace was maintained at 950°C in growing ZnF2 and
at 960°C in growing COO.06ZnO.94F2. The crucible was
lowered at a rate of 0.3 cm h-I in a temperature gradient
of 20 deg em-I. The charge in the crucible was heated
to the melting point in an atmosphere of HF. Before
the crucible was lowered to the position where crystal-
lization began, the HF supply was cut off and a slow
stream of dry N2 was passed through the furnace. The
CoF2 crystal used in our measurements had been grown
in a similar fashion by Matarrese24 in this laboratory.
Samples for spectroscopic measurements were cut from
the boule with a silicon carbide wheel and oriented to
within 0.5° with x rays. Parallel faces spaced at the de-
sired thickness were ground with silicon carbide paper.
The faces were polished with a water slurry of Linde
B-5125 Al20 3 powder. To prepare the very thin crystals
of CoF2 a special brass jig was constructed which main-
20 A. I. Belyaeva, V. V. Eremenko, N. N. Mikhailov, and S. V.
Petrov, Zh. Eksp. Teor. Fiz. 49, 47 (1965) [SOy. Phys.-JETP
22,33 (1966)].
'I R. F. Blunt, J. Chern. Phys. 44, 2317 (1966).
22 J. W. Stout and E. Catalano, J. Chern. Phys. 23, 2013 (1955).
'3 M. Griffel and J. W. Stout, J. Am. Chern. Soc. 72, 4351
(1950).
24 L. M. Matarrese, "The Magnetic Anisotropy of Iron Group
Fluorides," thesis, University of Chicago, 1954 (unpublished).
 4198 L. J.
I I r I 1 1
D=log
10
1.9
I analysis, and sample 5, which had four polished surfaces,
1.5
.'.
1.0 •*
e
o logarithm (base 10) of the ratio of the intensity of
o through the sample, thus obviating the need for correc-
A tion for surface reflections. The crystal holder was
* . x
o
0.5
FIG. 1. Absorbance (D) versus wavelength measured on
different instruments with sample 6 at 300o K. The points indicated
by 0, e, and X are from three different spectrophotometer charts
measured with the Beckman DK-1, and those indicated by
are from densitometer readings of a photographic plate exposed
on the Wadsworth mounting spectrograph.
tained parallelism of the two surfaces. The thickness of
the crystals was measured with a micrometer, and
checked by measurements of the weight and cross sec-
tional area.
The concentration of C02+ in the COO.06ZnO.94F2 crystal
varied by a factor of l.13/mm along the axis of the
boule and by a factor of 1.0l/mm perpendicular to the
boule axis. This concentration gradient was measured
by observing with a Cary spectrophotometer the varia-
tion in the room-temperature absorbance at 5300 A of
a flat crystal slab. The mean concentrations of the sam-
ples used were determined by comparing their absorb-
ance per unit thickness with that of sample 8, which
was dissolved and analyzed for cobalt by the colori-
metric (NH4) 2Co(SCN) 4 complex method. 25 The
analytical method was checked with weighed mixtures
of powdered ZnF2 and CoF2. The error in the composi-
tion of samples is estimated as 5%.
The properties of the crystal samples studied are
2' E. B. Sandell, Colorimetric Determination of Traces of Metals
(Interscience Publishers, Inc., New York, 1959), 3rd ed., p. 422.
ZIMRING AND J. W. STOUT
listed in Table I. The spectra of COO.06ZnO.94F 2 were
measured with samples 6 and 7. Sample 8 was used for
was used to compare the 7r-rr and a absorbance per unit
thickness at 5300 A in order to determine the composi-
tion of sample 6. The order of magnitude of trace im-
purities present was determined by spectrochemical
analysis, and the results are given in Table II.
Apparatus and Procedures
The sample whose spectrum was to be measured, to-
gether with the crystal of ZnF2, was mounted on a
crystal holder having two matched circular apertures
of diameter 0.48 cm. The absorbance was taken as the
light transmitted through the ZnF2 crystal to that
mounted in a glass Dewar with optically flat Pyrex
windows, and was accurately aligned relative to the
light beam and the polarizers. Liquid N2 or liquid H2
was added to the Dewar for the low-temperature
measuremen ts.
Beckman DK-1 and Cary Model 14 spectrophotom-
eters were used to record the spectra in the 5000-16 000
cm-1 region and for check measurements in the 16 000-
25000 cm-1 region. Most of the measurements in the
last spectral region were made with a Wadsworth
stigmatic-mount grating spectrograph. 26 ,27 The spectra
were recorded on photographic plates whose optical
+ density was measured with a densitometer. For spec-
troscopic plates, two different exposures of the ZnF2
blank permitted the slope of the optical density versus
log of the intensity curve for each plate to be deter-
mined. The two different blank intensities were ob-
tained by using a rotating sector disk of a known
(variable) aperture. The two blank intensities were
chosen such that the optical density of the sample
spectrum was intermediate between those of the two
blanks and on the linear portion of the curve. All ex-
posures on a given plate had the same exposure time.
With the Wadsworth spectrograph, rr and 7r spectra
were photographed simultaneously; the two beams of
perpendicular polarization were separated by a Wolla-
ston prism and formed distinct images on the slit.
With the recording spectrophotometers, polarizing
prisms were rotated to obtain the two polarized spectra.
Figure 1 illustrates the agreement between absorbances
of a sample measured in the 4000-6000 A region with
the Beckman DK-1 spectrophotometer and with the
grating spectrograph. Further details are given in the
thesis of the first author.28
26 J. w. Stout, J. Chern. Phys. 31, 709 (1959).
27 G. R. Harrison, R. C. Lord, and J. R. Loofbourow, Practical
Spectroscopy (Prentice-Hall, Inc., New York, 1948), p. 85.
28 L. Zimring, "Crystal spectra of CoF2 and CoF2 in ZnF2,"
thesis, University of Chicago, 1964 (unpublished).
 CRYSTAL SPECTRA OF CoF. AND COo.o6Zno.94F. 4199

E liter em'. mole'

0.3

em'
FIG. 2. Molar extinction coefficient. versus wavenumber measured with different instruments and samples. Curves marked (1)
were obtained with a Cary spectrophotometer and sample 3. Curves marked (2) were obtained with a Beckman DK-l spectrophoto-
meter and sample 2. Curve (3) is with a Cary spectrophotometer and sample 5, and curve (4) is with a Cary spectrophotometer and
sample 7. In this and succeeding figures, P stands for CoF2, D for COo.oeZno.94F2, R for T=300oK, N for T= 77°K, and H for T=20.4°K.
1r, fT, and a indicate different polarizations. The molar extinction coefficients read from the curves in Figs. 2-17 should be multiplied
by 0.96 for the CoF2 sample and by 0.98 for the Co o.o6 Zno. 94F2 sample to obtain best values (see text).

E I iter em'. mOle'

2.0

15

eni'
o
FIG. 3. Molar extinction coefficient. versus wavenumber. CoF2 at 300 K. See caption of Fig. 2 for code.
4200 L. J. ZIMRING AND J. W. STOUT

14000

2.5 € liter criil.mole l

2.0

1.5

10000 15000 20000 25000

o
FIG. 4. Molar extinction coefficient e versus wavenumber. COo.o6Zno.94F2 at 300 K. See caption of Fig. 2. for code.

€ I iter cm-l. mole-l

CoF2 and CoF2 in ZnF2

1.0

0.5

8000 9000
o
FIG. S. Molar I!xtinction coefficient e versus wavenumber. 14000 A band. CoF2 and COo.o6Zno.94F2 at 300 K. See caption of Fig. 2
for code.
 CRYSTAL SPECTRA OF CoF. AND Co O • 06 Z n O.94 F • 4201
o
16000 14000 12000 A

E liter em l• molel em l

FIG. 6. Molar extinction coefficient. versus wavenumber. 14000 Aband. COO.06ZnO.94F2 at 77 and 20.4°K. See caption of Fig. 2 for code.

1.0

FIG. 7. Molar extinction coefficient E versus wavenumber. 14000 A band. (J" spectrum of CoF2 at 77 and 20.4°K. See caption of Fig. 2
for code.
4202 L. J. ZIMRING AND J. W. STOUT

8000 7000 6500

E liter eml.mole l
0.3

0.2

0.1

14000 16000 em l
FIG. 8. Molar extinction coefficient E:versus:wavenumber. 7000~A ban(of~CoF2. See caption of Fig. 2 for code.

o
8000 7000 6500 A

E liter eml.mole l
0.3

0.2

0.1

1. DR7T

14000 15000 16000 cml

FIG.~9. Molar extinction coefficient E versus wavenumber. 7000 A band of Co o.o.Zno.••F2. See caption of Fig. 2 for code.
 CRYSTAL SPECTRA OF CoF 2 AND COo.o6Zno.94F2 4203

TABLE I. Properties of crystal samples studied.

Light propagation
direction Co2+
Sample relative to Thickness concentration
number Composition tetragonal axis em molelitec1

2 CoF2 .L (,..,u) 0.090 47.4

3 CoF2 .L(,..,u) 0.0139 47.4
4 CoF2 II (a) 0.0157 47.4
5 COo.048ZnO.952F2 .L(,..,u) 0.256 2.28
II (a) 0.352 2.28
6 COO.061ZnO.939F2 .L (,..,u) 0.209 2.90
7 COO.053ZnO.947F2 II (a) 0.142 2.55
8 COo.051ZnO.949F2 II (a) 0.103 2.46
9 ZnF2 .L 0.189

RESULTS with propagation direction parallel to the tetragonal

axis of the crystal; 7r and u are spectra with propagation
The molar extinction coefficients were calculated direction perpendicular to the tetragonal axis and with
from the expression
the electric vector of the light parallel and perpendicular
e= (l/et) IOglO(IO/I) (1) to the tetragonal axis, respectively. In Figs. 2-17 the
molar extinction coefficients read from the curves
where 10 is the light intensity with the ZnF2 crystal in should be multiplied by 0.96 for the CoF2 sample and
the beam, and I, that with the sample in the beam. by 0.98 for the COo.OSZnO.94F2 sample to obtain best
The concentration of the Co2+ in moles per liter, c, and
the crystal thickness in centimeters, t, are listed in
Table 1. Figure 2 indicates the agreement obtained be- 6 00 5000 ~ 4000
tween different samples and different spectrophotom-
E liter eml . molii l eml
eters in the 12000-16000 cm-1 region. The values of
molar extinction coefficient obtained with various sam-
ples and instruments were plotted versus wavenumber
and composite curves drawn. These are presented in 2.0
Figs. 3-16. The curves are identified by a three-letter
code. The first letter P stands for pure CoF2, and D, for
Coo.OSZnO.94F2. The second letter R stands for T=
300o K; N stands for T= 77°K; and H stands for T=
20.4°K. The third letter a indicates an axial spectrum 1.5

TABLE II. Spectrochemical analysis of trace impurities in

samples studied. No As, Au, Bi, Be, B, Cd, Cr, Ga, Ge, Hg,
In, Li, Mo, Pd, P, Pt, Pb, Sn, Sb, Te, Ta, TI, or Ti was found in
any sample. Cobalt was not found in sample 9 and Zn was not
found in samples 2, 3, and 4.

Weight percent in sample

Element 2,3,4 5,6,7 8 9

Al 0.001 0.01 0.005

Ag 0.001 0.001
Ca 0.001 0.001
Cu 0.001 0.001 0.001
Fe 0.001 0.01 0.1 0.01
Mg 0.0001 0.01 0.01
Mn
Ni
0.001
0.001
cm l25000
Si 0.001 0.001 FIG. 10. Molar extinction coefficient E versus wavenumber.
V 0.001 0.01 5000 1. band, ,.. spectrum, of COO.06ZnO.94F. at various tempera-
tures. See caption of Fig. 2 for code.
4204 L. J. ZrMRrNG AND J. W. STOUT

TABLE III. Observed wavenumbers of broad peaks in absorption spectra of CoF2 and COO.06ZnO.9.F2 and
wavenumbers from octahedral field calculation (see text). T = 20.4 oK.

10-3 (ii, em-I)

Assignment CoF2 COO.06Zno.94F2 Calculated
of excited Dq=715 cm-l
state 11" u a 11" u a B=971 cm- l

'T2g ('F) 7.30 7.23 7.35 6.145

'A 2g (4F) 14.2-14.5 14.45 14.37 13.295
'T1g (4P) 19.27 19.05 19.05 19.30 19.10 19.15 19.700
20.60 20.7 20.65 20.70

values. These corrections, which are less than the ex-
perimental uncertainties, arise from a numerical error
discovered after the curves were drawn. Oscillator
strengths listed below in Tables V and VI have been
appropriately corrected. Figure 3 shows the 3000 K
spectrum of CoF2 in the three polarizations over the
spectral region 5000-25000 em-I, and Fig. 4 presents
the similar spectrum of Coo.osZno.94F2. The room-tem-
perature spectra of the 14000 A band (6000-9000
em-I) are given in more detail in Fig. 5, and the low-
temperature '/I' and (1" spectra of Coo.osZno.94F2 are in
Fig. 6. Figure 7 shows the (1" spectrum of CoF2 at low
temperatures. The axial spectra of both samples and
the '/I' spectrum of CoF2 were measured only at room
temperature in the 6000-9000 cm- I region.
The 7000 A band (12000-16500 em-I) of CoF 2 is
shown in Fig. 8. The a, (1", and '/I' spectra were measured
at 298°K, and the '/I' and (1" spectra at 77 and 20.4°K.
The small peak at 15 150 cm-I shown in the 298°K (1"
spectrum is possibly due to an impurity since it was
not seen in all samples (Fig. 2). Figure 9 gives the
spectra of Coo.osZno.94F2 in the 12000-16500 cm-I re-
gion. The only low-temperature spectra measured were
the (1" spectrum at 20.4°K.
The strongest absorption is the 5000 Aband (16500-
25000 em-I). The '/1', (1", and a spectra of Coo.osZno.94F2
at various temperatures are shown in Figs. 10-12, re-
spectively, and the corresponding spectra of CoF2 ap-
pear in Figs. 13-15. Figure 16 shows on a larger scale
the 20.4°K spectra of CoF2 and Coo.osZno.94F2 in the

6000 5000 A 4000 6000 5000 A 4000

E liter eml.moli l

2.0 2.0

1.5 1.5

1.0 1.0

0.5 0.5

20000 em l 25000 20000 _I 25000

ern
FIG. 11. Molar extinction coefficient E versus wavenumber. FIG. 12. Molar extinction coefficient E versus wavenumber.
5000 A band, u spectrum, of Coo.ooZnO.94F2 at various tem- 5000 A band, axial spectrum of Coo.OOZnO.94F2 at 300 and 20.4°K.
peratures. See caption of Fig. 2 for code. See caption of Fig. 2 for code.
 CRYSTAL SPECTRA OF CoF 2 AND COO.06ZnO.94F2 4205
0
6000 5000 A 4000 TABLE IV. Observed wavenumbers of narrow peaks in absorption
spectra of CoF2 and COo.06ZnO.94h. T=20.4°K.
E liter em'.moli' en;!
10-3 (v, em-I)

CoF2 COo.06Zno.94F2
1r q a 1r q a

20.05 20.05 20.05(?)

21.19
21.38 21.43 21.43 21.49 21.37 21.37
21.60 21.58 21.58
21.64 21.64 21.52 21.52
21.82 21.80 21.80 21.8 21. 79 21.79
21.97 22.02 22.02 22.00 22.00
22.16
22.768 22.768
22.93

21000-23000 cm-I region where considerable structure

was observed. Finally, we show in Fig. 17 the room-
temperature axial spectrum of COo.o6ZIl{).94F2 in the
range of 30000-45000 em-I. This region was not in-
vestigated in detail and the curve is presented primarily
to show the beginning of the fundamental absorption at
45000 em-I.
From examination of the curves, one sees that there
em' 25000 is a close correspondence between the spectra of CoF2
FIG. 13. Molar extinction coefficient E versus wavenumber. and COo.o6Zno.94F2, both in magnitude of the molar ex-
5000 A band, 1r spectrum of CoF2 at 300 and 20.4°K. See caption tinction coefficient and in frequency of the absorption
of Fig. 2 for code.
6000 5 00 4 00
6000 5000 4000
E liter eni'·moli l
E liter em l. mohil

2.0

1.5

25000 25000

FIG. 14. Molar extinction coefficient E versus wavenumber. FIG. 15. Molar extinction coefficient E versus wavenumber.
5000 A band, q spectrum for CoF2 at 300 and 20.4°K. See caption 5000 A band, axial spectrum for CoF2 at 300 and 20.4°K. See
of Fig. 2 for code. caption of Fig. 2 for code.
4206 L . .T. ZIMRTNG AND .T. W. STOUT

4700 4600 4500 4400

Co F2 and
CoF2 in ZnF2 E 1iter cn'il·moll!i

0.5

21000 21500 22000 23000

cm1
FIG. 16. Molar extinction coefficient E versus wavenumber. Structure in the 20AoK spectra of CoF2 and Coo.osZno .•,F2 between 21 000
and 23000 cm-I . See caption of Fig. 2 for code.

peaks. As a general rule, the two spectra agree within u and a spectra of CoF2 but is absent in the spectra of
the experimental uncertainties. There are, however, the dilute crystal.
differences in relatively sharp structures which are seen There are marked differences between the spectra in
in the 20.4°K spectra. Figure 16 shows that in the different polarizations. If the mechanism of the transi-
21000-23000 cm-l region the 20.4°K spectra of CoF2 tion involved only an electric dipole moment, the a
and COO.06ZnO.94F2 are significantly different in their and u spectra would be identical. This is nearly true for
detailed structure. The most striking difference is the the 5000 and 7000 Abands, but in the 14000 A band
sharp absorption at 22 768 cm-l which is present in the the u spectrum is significantly weaker than the a spec-
trum, indicating that some of the intensity in this band
arises from a mechanism involving the magnetic dipole
3500 3000 2500 moment.
I
I I
I
1 I I r i
E liter cm'.mole' DISCUSSION

Assignment of Bands
20

In CoF2 each COH ion is surrounded by six F- ions,

distorted in angle from a regular octahedron. l The ob-
served spectra are consistent with the pattern calcu-
lated by many investigators29 .3o for COH in an octahe-
10
dral field of negatively charged ligands. The 4F and 4p
terms of the free COH ion are split in a ligand field of

~ 29 A. Abragam and M. H. L. Pryce, Proc. Roy. Soc. (London)

~C=C=~L-L-L-L-L-~~~~L-~L-Lj~~
30000 40000 em'
AZ06, 173 (1951).
30 For references see (a) J. S. Griffith, The Theory of Transition
Metal Ions (Cambridge University Press, Cambridge, 1961),
FIG. 17. Molar extinction coefficient E versus wavenumber. Axial Chap. 11. (b) C. J. Ballhausen, Introduction to Ligand Theory
spectra at 300oK, Coo.osZno.9,F2 in the ultraviolet. (McGraw-Hill Book Co., New York, 1962), Chap. 10.
 CRYSTAL SPECTRA OF CoF, AND COO.06ZnO.94Ft 4207

TABLE V. Oscillator strengthsj of CoF, and COO.06ZnO.94F, for various polarizations and temperatures. The range is in units of 103 em-I.

Polarization
T
OK Sample a

5000 A band
298 CoF, jXlO' 23 37 37
Range 16.3-24.0 16.3-24.2 16.0-24.5
298 Cao.o6Zno.,.F2 jX10 6 22 40 37
Range 16.5-24.0 16.5-24.5 16.0-24.5
20.4 CoF2 jX10 6 15 19
Range 16.7-24.5 16.5-24.5
20.4 COO.06ZnO.94F2 jX106 13 18
Range 16.7-22.1 17.4-23.4
7000 A band
298 CoF, jX106 0.5 3.0 3.3
Range 12.9-16.0 12.0-16.0 11.4-16.4
298 jX106 1 2.5 3.0
Range 12.2-16.5 12.1-16.3 11. 5-16.4
20.4 CoF, jXIQ6 0.3 1.5
Range 12.9-16.1 12.9-16.5
20.4 fX10 6 1.4
'Range 13.1-16.5
14000 A band
298 CoF2 jX106 8.1 4.3 5.8
Range 5.7-9.7 5.2-9.5 5.5-9.5
298 COO.06ZnO.9.F2 jX10' 7.2 4.9 6.2
Range 5.4-9.1 5.4-9.4 5.5-9.5
77 CoF2 jXI06 2.3
Range 6.4-9.0
77 COO.06ZnO.9.F2 fX10 6 5.6 2.9
Range 6.3-9.3 6.4-9.0
20.4 CoF2 jXlO' 2.5
Range 6.3-9.2
20.4 COO.06ZnO.94F2 jX106 5.0 2.6
Range 6.3-8.9 6.2-9.1

octahedral symmetry into four levels: two 4TIg , a 4T2g , Dq, the lower energy 4TIg level, which is the ground
and a 4A2g, whose relative energies are given by level in the crystal, and the 4T2g and 4A 2g levels become
the 4F term of the free ion. The upper 4TIg level, which
E(4TIg) = -7.SB+SDq
is the highest quartet level in the CoF2 crystal, becomes
±[22SB2+ 180BDq+ 100(Dq)2Jl!2 the 4 P term of the free ion. We therefore assign the ab-
sorption in the 14000 A band to transitions from
E(4A2g) =20Dq, 4TIg(4F) to 4T2g(4F) , that in the 7000 A band to transi-
E(4T2o) = lODq. tions from 4TIg(4F) to 4A 2g (4F) , and the major absorp-
tion in the 5000 A band to transitions from the 4TIg(4F)
Here B is a Racah parameter and lODq is the one- to 4TIg (4P). This assignment is in agreement with
electron octahedral field splitting. In the limit of zero those of other investigatorsI2.13.14.19.21.31 and with that of
Ferguson, Wood, and Knox32 for KCoF3, the optical
spectrum of which is similar to that of CoF2.
TABLE VI. Oscillator strength j in the 21000-23000 cm-I In CoF2 the ground 4Tlg(4F) octahedral field level is
region from structure in excess of smooth curves drawn on the
high-wavenumber side of peaks at 20.7XI03 cm-I (0', a) and split2 ,33 by the combined effects of spin-orbit coupling
19.3XI03 cm-I (.".). T=20.4°K. and the orthorhombic crystal field into six Kramers
doublets, which are further split by the molecular field
Polarization in the antiferromagnetically ordered state. Electronic
21 000-23 000 cm-I
Sample .". 0' a transitions among levels arising from 4TIg(4F) are ob-

CoF2 0.6X1Q-6 1.1XIO-s 1.5XIQ-6 31 L. F. Johnson, R. E. Dietz, and H. J. Guggenheim, App!.

Cao.o,Zno.9.F2 0.3XlO-s 0.6XlO-6 0.8X1o-'
Narrow line at Phys. Letters 5,21 (1964).
32 J. Ferguson, D. L. Wood, and K. Knox, J. Chern. Phys. 39,
22 768 em-I, CoF2 2XIO-S 2X1O-S 881, (1963).
33 H. M. Gladney, Phys. Rev. 146,253 (1966).
4208 L. J. ZIMRING AND
served28 ,34--36 in the 700-1500 cm-l infrared spectra. The
observed transitions at 20.4°K are from the ground
level in the CoF2 crystal which will be about SOO cm-I
lower than the center of energy of the 4TIg(4F) group.
From the shape of the observed spectra and the close
agreement between the spectra of CoF2 and
COO.06ZnO.94F2, one can conclude that the observed
spectra include energy of vibrational excitation, both
the excitation of optically active lattice vibrations37 ,38
to provide the mechanism for electric dipole transitions,
and the Franck-Condon overlaps of the ground vibra-
tional states with vibrational states of the excited
electronic levels in the case of magnetic dipole transi-
tions. The peaks of the observed spectra will include a
vibrational energy of the order of 700 cm-l . We expect,
therefore, that the observed peak positions of the
spectra of CoF2 at 20.4°K will lie between 1000 and
1500 cm-l higher than those calculated for an octahe-
dral field without vibrational excitation with appropri-
ate values of Dq and E.
The best value of Dq is obtained from the difference
of the observed peak values of the transitions to the
4T2(4F) and 4A2(4F) states since this difference does
not involve the Racah parameter E, and the effects of
the splitting of the ground 4TIg(4F) states and of vibra-
tional excitation should largely cancel. From the ob-
served separation we calculate Dq= 715±20 cm-I • The
observed peak frequencies of CoF2 and COO.06ZnO.94F2 at
20.4°K are given in Table III together with those cal-
culated from Dq= 715 cm-l and with the value E=
971 cm- I obtained from the separation39 of the 4 F and
4p levels of the free ion. For the reasons discussed
above, the wavenumbers of the peaks in the transitions
from the ground level to the 4T2g(4F) and 4A2g(4F)
levels lie about 1100 cm-I above those calculated for an
octahedral crystal field without vibrational excitation.
The transitions to the 4T1g (4P) states are strongly
polarized with one prominent peak at 19.27X 103 em-I
in the 7r spectrum and two prominent peaks at 19.05
and 20.60X 103 cm-l in the (J" and a spectra of CoF2.
The spectra of COO.06ZnO.94F2 are very similar to those
of CoF2 in this region. The splitting into three peaks
and the strong polarization presumably arise from the
separation of the three orbital levels of the 4T1g (4P) by
the crystal field of D2h symmetry. The mean position of
the three peaks in the transitions to the 4T1g (4P) levels
is close to that calculated for an octahedral field, al-
though as discussed above, it is expected to be 1000-
1500 cm-I higher. The reason is probably that because of
34 R. Newman and R. M. Chrenko, Phys. Rev. 115, 1147
(1959) .
3Ii A. I. Zvyagin, V. V. Eremenko, and V. I. Kut'ko, Fiz. Tverd.
Tela 7,3102 (1965) [Sov. Phys.-Solid State 7,2505 (1966)].
36 D. Simkin and J. W. Stout (private communication).
37 A. S. Barker, Jr. and J. A. Ditzenberger, Solid State Commun.
3,131 (1965).
38 M. Balkanski, P. Moch, and G. Parisot, J. Chern. Phys. 44,
940 (1966).
39 C. E. Moore, Nat!. Bur. Std. Circ. 467,2,85 (1952).
J. W. STOUT
mixing with near-lying doublet states and with charge-
transfer states of the crystal, the 4T1 g( 4 P) level is
lowered in energy. Ferguson, Wood, and Knox3 have
calculated that in KCoF3 and KMg(Co)F3 this state
has of the order of 10% doublet character.
The 2G, 2H, 2P, and 2D levels of free Co2+ ion lie low
enough in energy so that levels arising from them may
appear in the spectral range below 25 000 cm-I . The
positions of these levels in an octahedral field have been
calculated by several investigators. 32 ,4o,41 In CoF2 there
will be a large number of doublet levels between 16 000
and 25000 cm-r, and the exact calculation of the posi-
tions of these levels would require a more accurate
knowledge of the crystal-field parameters, including the
effects of spin-orbit coupling and orthorhombic crystal
fields, than is now available. In Table IV we list the
positions of observed peaks in the spectra of CoF2 and
COO.06ZnO.94F2, without attempting an assignment.
The sharp peak at 22 76S±1 cm-I which had a width
on the spectroscopic plate of 10 cm-r, appears only in
the (J" and a spectra of CoF2 and is therefore an electric
dipole transition. Since this line does not appear in the
spectrum of COO.06ZnO.94F2, it must derive its intensity
from a pair-interaction mechanism. 42 This line has been
observed by Eremenko and Belyaeva15 and by Van der
Ziel and Guggenheim,19 who identified it as a magnon
sideband, in agreement with the earlier suggestion I7 ,18
based on measurements of the Zeeman splitting.
Although the positions of the peaks between 21000
and 23000 cm-I are different for CoF2 and
COO.06ZnO. 94F 2 (Fig. 16), both crystals show absorption
in this region. It is probable that the transitions in this
region are to doublet levels which may contain about
10% quartet admixture. 32 In such a case one expects an
electric dipole transition involving odd vibrations to be
stronger than the pair-interaction mechanism and thus
comparable absorption in the pure and dilute crystals.
Oscillator Strengths
Oscillator strengths were calculated from the curves
of molar extinction coefficient versus wavenumber with
the expression f =4.32 X 10--9f E dli. No correction was
made for the index of refraction of the crystal. The
oscillator strengths for the various bands are listed in
Table V. Within the experimental uncertainties the
oscillator strengths for corresponding bands and polari-
zations are the same in CoF2 and COO.06ZnO.94F2' This
indicates that the transition mechanism is a single-ion
one and does not involve pair interactions. In the
5000 and 7000 A bands, the 29SoK oscillator strengths
for the (J" and a spectra agree within experimental error
and are larger that the 7r oscillator strength, indicating
that these transitions are principally electric dipole in
40 Y. Tanabe and S. Sugano, J. Phys. Soc. Japan 9, 753, 766
(1954).
41 W. Low, Phys. Rev. 109, 256 (1958).
42 D. S. McClure, J. Chern. Phys. 39, 2850 (1963).
 CRYSTAL SPECTRA OF CoF 2 AND Co o .o 6 Z n o.94 F • 4209

nature. The variation of oscillator strength of these
bands between 298 and 20.4°K is consistent with that
calculated43 for an electric dipole transition involving
excitation of odd lattice vibrations with frequencies in
the range of the infrared-active lattice vibrations37 ,38 of
CoF2. Since CoF2 excited electronic states are occupied
at 298°K, a reliable estimate of the vibrational fre-
quency cannot, however, be obtained from the tem-
perature variation of oscillator strength.
The oscillator strengths at 298°K for the 14000 A
band of CoF 2 and COO.06ZnO.94F2 show clearly that there
is a contribution to the intensity from magnetic dipole
transition moment. From the oscillator strengths in
Table V, one may set limits to the contributions in the
14000 A band of the electric dipole transition moment
parallel to the tetragonal crystal axis (Ell) and the
43 Reference 30(b), p. 187.
magnetic dipole transition moment perpendicular to
this axis (H J.). In units of oscillator strength, jX 106
these are for CoF2 6.6~EII~2.3 and 5.8~HJ.~1.5,
and for COo.OSZnO.94F2 5.9:2:EII:2:1.0 and 6.2:2:HJ.~1.3.
Upper limits to HII and EJ. are the oscillator strengths
for the 0' spectrum. The uncertainties in jX 106 are
estimated to be about 0.4.
Oscillator strengths for the structure seen at 20.4°K
in the 21 OOQ--23 000 cm-1 region are listed in Table VI.
In obtaining these values, a background smooth curve
drawn on the high-wavenumber side of the broad peaks
at 20.4XI03 cm-1 (0', a) and 19.3XI03 cm-1 (11') has
been subtracted. The oscillator strength of the narrow
line at 22 768 cm-l is also listed in Table VI.
ACKNOWLEDGMENT
We thank Miss M. Batchelderfor the spectrochemical
analyses.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 51, NUMBER 10 15 NOVEMBER 1969

On Symmetric Multicomponent Diffusion Coefficients

D. W. CONDIFF

Department of ChemicaJ Engineering, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213

(Received 21 July 1969)

The symmetric set of isotropic multicomponent diffusion coefficients introduced by Curtiss in the context
of the kinetic theory of dilute gases are given a general definition and shown to possess general symmetry
properties by virtue of Onsager reciprocal relations. Their relationships to Onsager coefficients, Curtiss-
Hirschfelder diffusion coefficients, and Bearman-Kirkwood multicomponent friction coefficients are
established and employed in stability considerations to deduce results which include the vanishing of
Curtiss-Hirschfelder thermal diffusion coefficients in dilute solution as a consequence of the second law of
thermodynamics.

In a recent publication Curtiss1 has reconsidered the
original Curtiss-Hirschfelder formulation2 of the theory
of multicomponent molecular diffusion in isotropic
gases. In re-examining the Chapman and Enskog3
normal solution of the multicomponent Boltzmann
equation for dilute gases he has established that it is
possible and convenient to work, in the kinetic theory,
with a set of redefined diffusion coefficients which are
symmetric in the indices and diagonally positive, these
properties being a direct consequence of the definiteness
and symmetry properties of the brace integrals.
It is natural to inquire as to the limits of applicability
of this formulation for its practical advantages alone.
In addition, if possible, it is desirable to divorce the
symmetry properties of the diffusion coefficients from
those of brace integrals in view of the fact that the
kinetic theory of polyatomic gases readily admits to
molecular models (e.g., the rough sphere model3)
which retain the H theorem and Onsager-type reciprocal
relations despite a conspicuous but innocuous absence
of general symmetry properties among the brace (or
bracket) integrals. 4 Moreover, in the kinetic-theory
treatment5 of orientation specific transport mechanics,S
the corresponding orientation specific brace integrals
are unsymmetrical for the nonspherical molecular
models (e.g., loaded spherocylinders) as a general rule.
Whether or not one should then expect generalized
Curtiss coefficients, or Curtiss tensors, to retain their
properties and concomitant advantages in more
general circumstances is answered best by examining the

1 C. F. Curtiss, J. Chern. Phys. 49,2917 (1968).
2 C. F. Curtiss and J. O. Hirschfelder, J. Chern. Phys. 17, 550
(1949) .
3 S. Chapman and T. G. Cowling, The Mathematical Theory of
Non Uniform Gases (Cambridge University Press, Cambridge,
England, 1939).
4 D. W. Condiff, W. K. Lu, and J. S. Dahler, J. Chern. Phys.
42,3445 (1965).
6 W. D. Henline and D. W. Condiff, "Transport Mechanics in
Systems of Orientable Particles. II. Kinetic Theory of Orientation
Specific Transport for Hard Core Metals" (unpublished).
6 D. W. Condiff and H. Brenner, Phys. Fluids. 12,539 (1969).