Raman Spectra of the Rare Earth Orthophosphatest

G . M. Begun, G . W. Beall, L. A. Boatner and W. J. Gregor

Chemistry and Solid State Divisions, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, USA

Raman spectra of anhydrous crystalline samples of all of the lanthanide orthophosphates (with the exception of PmP04) have been obtained. These data were interpreted in a systematicmanner based on the known structures of these compounds. Assignments and correlations have been made for many of the observed bands.

INTRODUCTION
Orthophosphates formed by elements in the first half of the lanthanide transition series are structural analogs of the monoclinic mineral monazite. This mineral is characterized by an almost unique combination of properties that make its synthetic forms attractive as possible hosts for the long-term storage of radioactive actinide Accordingly, a series of investigations of the chemical and physical properties of the lanthanide (and related) orthophosphates is currently in progress. Single crystals of all of the lanthanide orthophosphates (except PmP0,) doped with small amounts of Gd3+ were prepared for the initial purpose of performing a series of electron paramagnetic resonance experiments. The availability of these samples made it possible to carry out a study of the Raman spectra for essentially the entire series of rare-earth orthophosphates. This study was directed toward the following objectives. First, baseline spectra were to be established that could be used as a basis of comparison with subsequent lanthanide orthophosphate crystals that would be doped with @-active actinides and, consequently, would be subjected to heavy-particle radiation damage. Second, a classification and correlation of the Raman spectra of the entire group of rare earth orthophosphates was desired. Yttrium orthophosphate was included in the present investigation because its properties are known to correlate well with those of the orthophosphates of the second half of the rare-earth series (i.e. TbP04 through LuP04) and also because Y P 0 4 is the analog of the natural mineral xenotime. In addition, a considerable literature exists on the properties of Y P 0 4 that can be used for the purposes of verification and comparison with the lanthanide compounds. The lanthanide orthophosphates can be conveniently divided into two groups on the basis of the prevalent crystal structural form. The first group has the monoclinic 'monazite' structure and consists of L a P 0 4 through GdP04. The second group has the zircon structure and consists of T b P 0 4 through LuP04. Both Y P 0 4 and ScP04 also crystallize with the zircon structure and can be grouped with the orthophosphates formed by
f A portion of this material was presented at the VIIth International Conference on Raman Spectroscopy at Ottawa, Canada, August 1980. See Proceedings VIIth International Conference on Raman Spectroscopy, ed. by W. F. Murphy, p. 88. North Holland Publishing Co., New York (1980).

elements in the last half of the lanthanide series. Promethium is not a naturally occurring element, and it was not practical to investigate the orthophosphate of this unstable nuclide. The Raman spectrum of crystalline Y P 0 4 has been reported by R i ~ h r n a nand Lazarev et aIa4 ;~ have presented the Raman spectra of YP04, H o P 0 4 and ErPO,. In the latter work, single crystal studies. were performed which enabled assignments of most of the frequencies to be made and attempts were also made to find systemati: variations with the atomic number. Yurchenko et al. have published Raman spectra of Y, Tb, Dy, Ho, Tm, Yb and Lu orthophosphates but many of the spectra are fragmentary and no significant attempt was made to systematize the results. The Raman spectrum of DyP04 has been published by Elliott et aL6 Reports of the Raman spectra of the Group I (i.e. lanthanum to gadolinium series) of rare earth orthophosphates were not found in the literature. The IR spectra of lanthanide orthophosphates have been fairly extensively studied. Infrared studies of YP04, HoP0, and E r P 0 4 are reported in Ref. 4 cited above, while the IR spectra of most of the Group I1 compounds accompany the Raman spectra in Ref. 5 . The IR spectra of most of the Group I and Group I1 orthophosphates were examined p y Hezel and Ross' in the spectral region 400-4000 cm- . Their work is part of a comprehensive study of 63 phosphates, sulfates and perchlorates. Portions of the IR spectra of La, Ce, Eu, Gd, Y and YbP04 have been reported by Tenisheva et a1.* Reflection IR spectra of L u P 0 4 and Y P 0 4 have been reported by Armbruster,' and the IR absorption spectrum of GdPO, is given by Petrov ef al.'"

EXPERIMENTAL
~~~~ ~ ~

Crystals of the lanthanide and yttrium orthophosphates were grown by dissolving and reacting lanthanide oxides in molten lead pyrophosphate at high temperatures." The L n P 0 4 crystals which formed on cooling were separated by dissolving the lead phosphate matrix in boiling concentrated nitric acid. Lanthanide oxides with a purity of 99.9% or better were used for all of the crystal preparations. The samples were doped by adding 0.1 wt% G d Z 0 3relative to the lanthanide oxide. The
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G. M. BEGUN, G. W. BEALL, L. A. BOATNER AND W. J. GREGOR

gadolinium impurity did not produce any detectable effects in the Raman spectra. Raman spectra were recorded with a Ramanor HG2S spectrophotometer (Instruments SA). This instrument employs a double monochromator with curved holographic gratings and photoelectric detection and pulse counting electronics. The spectra were excited with the 514.5, 488.0 or 457.9nm lines of a Spectra-Physics model 164 argon ion laser. The samples were generally in the form of small crystalline powders contained in melting point tubes. Some orientation effects were observed for the larger zircon-structure crystals, and some difficulties were encountered with the excitation of electronic bands, especially in the cases of Ce, Eu and Tb orthophosphates. By observing spectra with several different exciting lines, it was generally possible to distinguish the Raman spectra from the interfering electronic transitions. A few extraneous lines that were observed in some of the spectra in the 1100 cm-' region may be due to the inclusion of small amounts of meta- or pyrophosphates in some of the samples. Polarization studies were made on single crystals of L a P 04 and P r P 0 4 that were oriented, using Laue X-ray back reflection techniques, with the axis of symmetry perpendicular to both the incident and scattered light. Significant polarization effects were observed. It was not always possible, however, to distinguish between the A , and B , modes due to overlapping or unresolved combinations of the spectral bands.
1

t
c
0) C

2 .

C
H

L a PO4 Excitation 488.0 nml

I
Figure 2. Raman spectra of the Group It (Y, Tb,Dy, Ho, Er, Tm, Yb and Lu) orthophosphates. *=plasma lines.

C ~ P O ~ Excitotion 514.5 nm

RESULTS AND DISCUSSION

Pr PO4 Excitation 514.5nrn:

t
+ .C u)

a , +
C
I

Raman spectra of the group I (La, Ce, Pr, Nd, Sm, Eu and Gd) orthophosphates are shown in Fig. 1. Figure 2 presents the Raman spectra o the Group I1 (Y, Tb, Dy, f Ho, Er, Tm, Yb and Lu) compounds. Figures 3 and 4 show the results of polarization studies on a single crystal of PrP04. The frequencies of the observed Raman bands, their intensities, and our vibrational assignments are listed in Tables 1 and 2. A comparison of our results

Sm P o 4

I1

t
c

c (

I
2 ,

A Wavenumbers (ern-')
Figure 1 Raman spectra of the Group I (La, Ce, Pr, Nd, Sm, Eu . and Gd) orthophosphates.

A Wavenumbers (cm-')

Figure 3. Single crystal polarized Raman spectra of PrP04. X ( Z X ) V and X(ZZ)V.514.5 nm excitation.

E
I100

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RAMAN SPECTRA OF THE RARE EARTH ORTHOPHOSPHATES

A Wavenumbers (ern-')

Figure 4. Single crystal polarized Raman spectra of PrP04. X ( Y X ) Y and X(YZ)Y.514.5 nm excitation.

with the published data shows good agreement between our band frequencies for YP04, H o P 0 4 and E r P 0 4 and those published in Ref. 4. The spectrum of Dy P 0 4 shown in Fig. 2 is in excellent agreement with that presented by Elliott et aL6 Although there is considerable agreement, the Group I1 frequencies determined here do not coincide as well with the rather sketchy data of Ref. 5 for the Y, Tb, Dy, Ho, Tm, Yb and Lu orthophosphates. The present Raman observations may also be compared with the infrared observations of Hezel and Ross.' The free (P04)3pion has the four normal modes of vibration of a tetrahedral ion. These are: vl(Al), symmetric stretching; v3(F2), antisymmetric stretching;

v*(E) and v4(F2), bending vibrations. The Group I1 orthophosphates would be expected to have two frequencies, both IR and Raman active, in the P - 0 bond stretching region [the v 3 region of ion]. With the exception of 3 or 4 IR frequencies, very good agreement is found with these data. In the other regions no coincidences are expected between the Raman and IR data and this was found to be the case. The Group I orthophosphates present much more complicated IR and Raman spectra. The IR data of Hezel and Ross7 were used for comparison. The crystal site symmetry of the ion in this case indicates all of the frequencies should be both IR and Raman active. While a comparison of the IR and Raman data shows that there are numerous agreements, some frequencies are clearly not coincident. We attribute this lack of coincidences to factor group splitting which would give rise to mutual exclusion between the IR and Raman frequencies. This point may be illustrated by the frequency derived from ion where the the v1 symmetric frequency of the present assignments are consistently 20 cm-' above the IR assignments of Ref. 7 . The Group I1 (Y, Tb, Dy, Ho, Er, Tm, Yb and Lu) anhydrous orthophosphates crystallize with the tetragonal zircon structure. The crystals belong to space group 0:; (14:lamd).'* There are two molecules in the primitive cell. The Y ions and the groups occupy sites, while the oxygen atoms are located at sites with C, symmetry. The zircon structure and its vibrational modes are treated quite thoroughly by ' Dawson et ~ 1 . in~a paper dealing with the vibrational spectrum of ZrSi04. Factor group analysis gives the

Table 1. Experimental Raman frequencies (cm-') and relative intensities of the monoclinic, group I, lanthanide orthophosphates'
No
Lab
Ceb

PP

NdC

Smb

Eub

Gdb

25A 24A 23A 22A 20A 19A 18A 17A 16A 15A 14A 12A 11A 1O A 9A 8A 7A 6A 1A 2A 3A 4A 5A

gO(l.6) lOO(0.6) 120(0.2) 131(0.4) 151(0.5) 170(0.5) 183(0.3) 220(1.O) 227(1.I) 255(0.4) 271 (1.O) 394(0.9) 414(1.5) 465( 1.7) 537(0.4) 57 2(0.5) 589(0.3) 61g(0.8) 967(10.0) 991 (1.7) 1025(0.4) 1055(2.9) 1065(0.4) 1073(0.8)

88(1.5) lOO(1.0) 118(0.2) 129(0.7) 152(0.5) 172(0.6) 188(0.1) 21g(1.4) 227(1.l) 254(0.4) 270(0.9) 396(1.3) 414(1.8) 467(2.6) 536(2.5) 571(0.6) 589(0.3) 618(1.2) 970(10.0) 99011.7) 1024(0.4) 1054(3.4) 1070(1.1 )

90(1.7) 105(0.4) 122(0.2) 133(0.4) 158(0.5) 177(0.8) 188(0.1) 224(1.2) 230(sh) 251(0.4) 282(0.8) 399(0.9) 417(1.5) 469(2.0) 538(0.3) 572(0.4) 592(0.2) 623(0.9) 974(10.0) 994(1.) I 1028(0.4) 1058(3.7) 1075(1.0)

89(8.2) 106(2.3) 123(1.4) 133(3.1) 155(1.5) 164U.9) 180(4.0) 227(6.9) 230(sh) 263(2.3) 286(3.4) 399(3.8) 420(5.4) 470(5.7) 539(0.8) 574(1.7) 595(0.8) 625(3.0) 977(10.0) 997(1.7) 1032(0.7) 1062(5.2) 1079(1.9)

88(1.3) 107(0.5) 123(0.4) 132(0.6) 156(0.3) 170(0.5) 185(0.6) 2320.1) 242(0.6) 265(0.4) 294(0.4) 402(0.8) 423(1.2) 473(1.2) 538(0.3) 575(0.6) 595(0.4) 627(0.8) 982(10.0) 999(0.7) 1035(0.4) 1065(2.2) 1OSS(0.6)

87(1.8) 108(0.5) 124(0.5) 132(0.8) 158(0.3) 175(0.5) 189(0.7) 233(1.9) 244(0.9) 265(0.8) 310(0.7) 403(1.2) 423(0.7) 471 (2.3) 538(0.3) 576(0.5) 597(0.3) 629(1.0) 945(0.7) 989(10.0)

87U.4) 108(0.3) 123(0.4) 130(0.6) 158(0.2) 178(0.5) 192(0.5) ) 236(1.I 247 (0.6) 270(0.5) 308(0.4) 404(1.O) 429(0.4) 480(1.5) 540(0.3) 579(0.5) 599(0.3) 632(0.9) 987( 10.0) 1004(0.5) 1043(0.5) 1072(2.2) 1092(0.7)

1069(2.4) 1082(0.3) 1093(0.8)

All doped p i t h 0.1 wt.% Gd. Excitation: 514.5 nrn, 488.0 nm; sh =shoulder.
~

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G. M.BEGUN, G. W. BEALL, L. A. BOATNER AND W. J. GREGOR

Table 2. Experimental Raman frequencies (can-') and relative intensities of the xenotine type, tetragonal, group 1 , lanthanide 1 orthophosphates"
No.
Yb

Tbb

DyC

Hob

Erd

T d

YbC

L"b

Assignment

228 218 188 158 148 138 10B 88 66 18 28 38

a

96(0.2) 121(0.05) 157(0.7) 185(0.2) 210(0.1) 267(0.3) 299(3.0) 332(0.3) 484(0.9) 581 (0.8) 660(0.1) 1001(10.0) 1027(1.9) 1048(0.5) 1058(2.0)

130(1.1) 141(1.4) 183(0.3) 267(0.5) 293(3.0) 331 (0.7) 484(1.6) 576(0.6) 649(0.8) 995(9.6) 1014(2.7) 1043(sh) 1049(10.0)

132(0.4) 141(0.6) 185(0.1)

132(1.8) 141(1.5) 184(0.7)

{;:;I:::;

185(0.3)

c;;::::;
185(0.2) 266(0.3) 303(1.6) 330(0.1) 488(1.5) 580(0.6) 660(0.05) 1006(10.0) 1027(1.6) 1064(0.4)

98(0.05) 132(0.5) 138(0.5) 186(0.3) 268(0.5) 302(0.5) 330(1.O) 491(1.1) 582(0.5) 663(0.5) 1009(10.0) 1030(1.3) 1048(0.5) 1068(8.1)

138(0.3) 144(0.4) 191(0.3) &,(TI E, ( T ) Bi,(T)

295u.9) 331(0.7) 485(1.1) 578(0.4) 654(0.5) 998(10.0) lOlg(1.2) 1054(6.4)

297(10.0) 336U.6) 486(4.6) 578U.4) 656(0.5) lOOl(3.5) 1021(0.7) 1055(0.4)

300(3.3) 330(0.2) 477(2.0) 580(0.6) 659(0.1) 1004(10.0) 1024(1.9) 1061(1.4)

308(2.3) 334(0.6) 493(1.3) 587(0.7) 670(0.3) 101l(10.0) 1032(1.8) 1069(3.2)

E, ( T ) E,(R)
B2g Al,

4
6 9 1

Al,

4 7

8 19

All doped with 0.1 wt.% Gd. Excitation: 514.5 nm, '488.0 nm, 457.9 nm; sh =shoulder.

representation of the optical vibrations as

r = 2A1, T

+ A z n+4B1, +Bz, +5E, +A,,

+ 3A2, + B1, + 2Bzu +4E,.

This leads to Raman active frequencies as follows:

rEXT=2BIg+3E,: rINT=2A1g+2B1g+Bzg +2E,

for a total of twelve Raman vibrational bands. Lazarev et d4have made single cI ystal polarization studies of YP04, H o P 0 4 and ErP04 and assigned the observed Raman bands accordingly. We have followed their assignments and our data and assignments are tabulated in Table 2 for the Group I1 orthophosphates. Table 3 lists the correlation scheme for the phosphate stretching and bending modes between the isolated

Table 3. (Po4)'- group symmetry

Xenotime crystal symmetry
06,

Free ion
Td

Site symmetry
D2d

tetrahedral (P04j3- group, the (P0,j3- ion located at a DZd site, and the D4,, factor group splitting in the crystal. It can be seeq from the data of Table 2 that a simple site group analysis is not adequate to explain the spectra but that the factor group analysis fits quite well. The Group I (La, Ce, Pr, Nd, Sm, Eu and Gd) orthophosphates cr stallize with the monoclinic monazite [space group (P21/n)].12There are four molecules per unit cell. All atoms are located at general positions (Cl).Site group analysis predicts that all of the modes should be both IR and Raman active of Class A. This, however, does not agree with the data and a factor group analysis leads to the optical vibrations rT= 18A, + 18B, + 17A, + 16Bu. The Raman active = = frequencies are then: TINT 9A, + 9B,; rEXT 9A, + 9 B , for a total of 36 Raman active modes. For this group of lanthanide orthophosphates, at least 23 frequencies were observed. Since the groups are located at sites of C1 symmetry, site group analysis would yield 15 A modes, both IR and Raman active, whik factor group analysis yields 36 Raman and 33 IR active frequencies as stated above. Clearly there is considerable factor group splitting since a com arison of our data with the IR data of Hezel and Ross P shows an apparent coincidence between the IR and Raman bands in only 5 out of 13 observed IR bands. An assignment of the observed bands to A, or B , symmetry has been made in Table 1. This assignment is not unequivocal since some of the bands are clearly not split or are unresolved. Where both A, and B, symmetry are listed, either a distinction was not possible or both components are present. In order to classify the data systematically it is interesting to plot the variation of the observed frequencies of the various vibrations versus the atomic number or the crystal radii of the lanthanide ion. Figures 5 and 6 are plots of the symmetrical stretching frequencies of the (P04)3-group (no, 1A and lB, respectively in Tables 1 and 2) versus atomic number and versus crystal radii. The crystal radii were taken from Ref. 17. The data point for yttrium does not fall on the curve in the atomic number plot but falls nicely on the line near Ho when the crystal radii are used. The symmetric stretching
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276 JOURNAL OF RAMAN SPECTROSCOPY, VOL. 11, NO. 4, 1981

RAMAN SPECTRA OF THE RARE EARTH ORTHOPHOSPHATES

I
I008 1004 -

1000 -

::::I
I055

'5
1

996 992988
-

0) 3

r=

984 980 976 972 968

:
I s

1025 1020 1015

//
1
I

1010
1005

3 9 ' 57

A
-1

964l

'

I000

59

61

63

65

67

69

71

I I
990 985

A t o m i c number

Figure 5. Symmetric stretching frequencies for rare earth orthophosphates v. atomic number.

57 59 61 63 65 67 69 71 A t o m i c number

frequency of the (P04)3- ion in the crystals increases f linearly with the atomic number or crystal radius o the lanthanide ion from 967 cm-' in LaP04 to 101 1 cm-' in LuP04. In contrast, the symmetric stretching frequency o the f ion in the free state has a value14 of 938 cm-'. Two series of peaks are found that are derived from the v3 antisymmetric stretching mode of the (P04)3- ion at 1017 em-'. These are the 2A-2B and 3A-3B series shown in Fig. 7. In addition to these graphs the 4A and
1015

stretching frequencies for rare Figure 7. Antisymmetric earth orthophosphates v. atomic number.

1010
1005 I000 995 990 985 980

:'

a_
g
0)

ZI

Nd
975 970

7
Lo
32
I I 1 128 124 120 16 1 Crystal r o d i i of M+3 (pm) I

965

12 1

Figure 6. Symmetric (P04)3- stretching frequenciesfor rare earth orthophosphates v. crystal radii.

5A series (see Table 2) must be due to a splitting of the antisymmetric stretching frequency of the ion. All the frequencies increase regularly with increasing atomic number. bending frequencies the In the region of the frequencies 6A and 6B, 8A and 8B, and 10A and 10B are plotted in Figs 8 and 9. In a manner similar to the stretching modes, the frequencies of these bands increase regularly as one progresses to the higher molecular weight orthophosphates. In the region of the lattice vibrations, correlations are more difficult, and 18A and B and 22A and B have been plotted (Fig. 9) as representatives. In this region a slight tendency for the vibrational frequencies to increase with atomic weight is still found but is not nearly so marked as in the case of the higher frequencies. Efforts to find systematic trends were made by who concluded on the basis of their data Lazarev et d4 that most of the frequencies decreased with increasing atomic number. These authors calculated force constants to support this contention. The results of the present investigations, however, clearly show that the dominant trend is in the opposite direction. This effect has also been observed" in the lanthanide trihydroxides deforwhere the Ln-OH stretching and Ln-0-H mation frequencies were found to increase monotonically from La to Dy with the atomic number of the rare earth element. The trend is very marked in the P-0 stretching vibrations, still present in the 0-P-0 bending vibrations and slight in the lattice vibrations. The crystal radii of the lanthanide ions in most crystalline compounds have been found to decrease17 with increasing atomic mass of the ion. Crystal radii are plotted in Fig. 6. This lanthanide contraction results in a ion groups as one proceeds closer packing of the
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G. M. BEGUN, G. W. BEALL, L. A. BOATNER AND W. J. GREGOR

665

195

660 655

650 645 640 -

185

4 180

lo
O A

o o o o o

1
A

Q 620
615

635

625
I30
A A

A A A A A

1 2 5 t I
57

22A I I
59 61

228

I
63

,
65

I
67 69

585 5801 575

71

Atomic n u m b e r Figure 9. Lattice modes of ( P o p v. atomic number for rare earth orthophosphates.

570

485 4 9 . 480 475

470

o/

4
l o ,
I

465
57 59 61 63 65 67 69 71

atomic number lanthanide phosphates. The data show no evidence for a Ln-0 bond in the crystals. In summary, Raman spectra have been obtained for all of the anhydrous lanthanide orthophosphates except PmP04 and for YP04. These spectra have been correlated with the crystal radii and lanthanide atomic numbers and systematic variations were established.
Acknowledgements
Research sponsored by the Division of Material Sciences, Office of Basic Energy Sciences, US Department of Energy, under contract W-7405-eng-26 for Union Carbide Corporation. W.J.G. is a graduate student at the University of Tennessee, Department o Chemistry, f Knoxville, TN 37916, supported by the Division of Chemical Sciences, US Department of Energy, under contract DE-AS05-76ER04447 with the University of Tennessee (Knoxville).

Atomic number
Figure 8. Bending modes of earth orthophosphates.
v. atomic number for rare

from LaP04 to LuP04. The compression of the ion then shortens the P-0 distance yielding higher stretching and bending frequencies for the higher

REFERENCES
1. L. A. Boatner, G. W. Beall, M. M. Abraham, C. B. Finch, P. G. Huray and M. Rappaz, in The Scientific Basis for Nuclear Waste Management, Vol. 11, ed. by C. J. Northrup, p. 289. Plenum Press, New York (1980). 2. L. A. Boatner, G. W. Beall, M. M. Abraham, C. B. Finch, R. J. Floran, P. G. Huray and M. Rappaz, in The Management of Alpha - Contaminated Wastes, IAEA-SM-246173, lnternational Atomic Energy Agency, Vienna, Austria (in press). 3. I. Richman, J. Opt. SOC. Am. 56, 1589 (1966). 4. A. N. Lazarev, N. A. Mazhenov and A. P. Mirgorodskii, lzvest. Akad. NaukSSSR Neorgan. Mater. 14,2107 (1978). 5. E. N. Yurchenko, E. B. Burgina, V. I. Bugakov, E. N. Muravev, V. P. Orlovskii and T. V. Belyaevskaya, Izvest. Akad. Nauk SSSR Neorgan. Mater. 14,2038 (1978). 6. R. J. Elliott, R. T. Hanley, W. Hayes and S. R. P. Smith, Proc. R. SOC. Lond. Ser. A. 328,217 (1972). 7. A. Hezel and S. D. Ross, Spectrochim. Acra 22.1949 (1961). 8. T. F. Tenisheva, T M. Pavlyukevich and A. N. Lazarev, Izvest. . Akad. Nauk SSSR Seriya Khimich. No. 10, 1771 (Oct. 1965). 9. A. Armbruster, J. Phys. Chem. Solids 37, 321 (1976). 10. 11. 12. 13. 14. 15. 16. 17. 18. I. V. Tananaev, V. G. Pervykh and S. M. Petrushkova, Zh. Neorg. Khim. 12, 2645 (1967). R . S. Feigelson, J Am. Ceram. SOC. 257 (1964). . 47, R . W. G. Wyckoff, Crystal Structures, 2nd Ed., Vol. 111, pp. 15 and 33. Wiley-lnterscience, New York (1965). I. Krstanovic, 2.Kristalogr. 121, 315 (1965). P. Dawson, M. M. Hargreave and G. R . Wilkinson, J. Phys. C. 4, 240 (1971). G. W. Beall, L. A. Boatner, D. F. Mullica and W. 0. Milligan, J. Inorg. Nucl. Chem. 43, 101 (1981 ). F. Weigel, V. Scherer and H. Henchel. J Am. Ceram. SOC. . 48, 383 (1965). R. D. Shannon and C. T. Prewitt, Acta Crysrallogr. Sect. 8 25, 925 (1969). B. I. Swanson, C. Machell, G. W. Beall and W. 0. Milligan, J. Inorg. Nucl. Chem. 40,694 (1978).

K. I. Petrov,

Received 26 November 1980

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