J. inorg,nucl.Chem., 1973.Vol.35, pp. 1531-1534. PergamonPress.

Printedin Great Britain

SOLID STATE VIBRATIONAL SPECTROSCOPY- I I I [1 ]

T H E I N F R A R E D A N D RAMAN SPECTRA OF T H E BISMUTH(Ill)
OXIDE HALIDES

J. E. D. DAVIES
Department of Chemistry, The University of Lancaster, Lancaster

(Received 25 July 1972)

Abstract--The i.r. and Raman spectra of the bismuth oxide haiides, BiOCI, BiOBr, and BiOl, have
been recorded over the range 40-600 cm -1. Four bands are observed in the i.r. spectra of all three
compounds in agreement with the predictions based on the D4~ space group. Six bands are expected
in the Raman spectra of all three compounds. Only the spectrum of BiOBr contains six resolved
Raman bands, and an assignment is proposed for the observed bands.

INTRODUCTION
LECOMTE and Duval[2] carded out an i.r. study of bismuth oxide chloride in
1945. They claimed to have observed one band in 1586 cm -1 which was assigned
to the v ( B i ~ O ) mode of molecular O~---Bi--CI. These authors were apparently
unaware of previous crystallographic studies[3, 4] which indicated that the
bismuth oxide halides did not have a molecular structure, but rather an ionic
structure of space group D4~[, with 2 molecular formulae per unit cell. The
correlation method of Fateley et al. [5] indicates that for such a structure the
optical modes are as follows:
F = 2,41o+ 2 A 2 u + B l u + 3Eg+ 2Eu
the g modes being Raman active only, and the u modes being i.r. active only.
Bonnaire [6] reported four i.r. bands in the spectrum of BiOI whilst Rulmont
[7] has reported four similar bands for the chloride and the bromide. In this paper
we report the i.r. and Raman spectra of the three bismuth oxide halides over the
range 40-600 cm -~. Spectroscopic studies have been reported for compounds
such as the lanthanide oxide halides[8] and BaCIF and BaBrF[9, 10] which are
isostructural with the bismuth oxide halides. The assignments proposed in these
studies will obviously be of relevance to the present work.
1. J. E. D. Davies and D. A. Long, J. chem. Soc. (A), 1275 (1971).
2. J. Lecomte and C. Duvai, Bull. Soc. chim. Fr. 91 (1945).
3. F. A. Bannister, Mineral. Mag. 24, 49 (1935).
4. L. G. Siilen, Svensk. Kern. Tidskrift 53, 39 (1941).
5. W . G . Fateley, F. R. Doolish, N. T. MeDevitt and F. F. Bentley, Appl. Spectry 25, 155 (1971).
6. R. Bonnaire, C.r. hebd. S ~anc. A cad. S ci., Paris 266B, 1415 (1968).
7. A. Rulmont, C.r. hebd. S Janc. A cad. S ci., Paris 272B, 1364 (1971).
8. L.J. Basile, J. R. Ferraro and D. Gronert, J. inorg, nucl. Chem. 33, 1047 (1971).
9. J. F. Scott, J. chem. Phys. 49, 2766 (1968).
10. H. E. Rast, S. A. Miller and H. H. Caspers, J. chem. Phys. 55, 1484 (1971).
1531
1532 J.E.D. DAVIES

RESULTS AND DISCUSSION

T h e i.r. spectra recorded in the present work are shown in Fig. 1 and the wave-
number values are compared with previous data in Table 1. F o u r i.r. bands were
observed in each case and the present wavenumber values are in good agreement
with previous data.

Table l. lnfraredspectraofthebismuthoxidehalides(valuesincm -1)

BiOCI BiOBr BiOI Assignment

528* 529~ 524~ 520* 520~ 512~ 487* 488~ A2u

285 283 289 265 263 265 249 248 Eu
186 185 125 125 103 105 A~u
111 102 68 72 57 62 Eu

*Ref. [6].
t Ref. [7].
:~This work.

I ~ I , f i I R I i I f J i I i
40 ao ~2o mo 200 240 2ao 320 360 400
Wavenumber, crn-I

Fig. 1. Infrared spectra (40-400 cm -1) of nujol mulls of (a)BiOI, (b) BiOBr, (c) BiOCI.

T h e i.r. bands fall into two groups, the halogen insensitive and the halogen
sensitive bands. T h e former are assigned to motions involving the oxygen atoms
and the latter are assigned to motions involving the halogen atoms. T h e assign-
ment shown in Table 1 is the one proposed by Rulmont [7] from an i.r. study of
oriented films of BiOCI and BiOBr. F r o m this study Rulmont also proposed that
the assignment of Basile et al. [8] for the isostructural lanthanide oxide halides
should be modified. T h e assignment of Rulmont is in agreement with the assign-
ment proposed by Rast et al. [I0] from an i.r. study of an oriented film of B a B r F
which is also isostructural with the bismuth oxide halides.
 Vibrational spectra of the bismuth oxide halides 1533

The Raman spectra obtained in the present work are listed in Table 2 and the
spectra of BiOCl and BiOBr are illustrated in Fig. 2. Six Raman bands are
expected for these compounds, but only the spectrum of BiOBr contains six
resolved Raman bands.
The Raman spectra, like the i.r. spectra, consist of halogen sensitive and
halogen insensitive bands. This is in contrast to the spectra of the~lanthanide
oxide halides where Basile et al. [8] did not find any halogen sensitive Raman
bands.
The present spectra do however resemble the Raman spectra of BaCIF and
BaBrF in having halogen sensitive and halogen insensitive bands. Scott[9] has
given descriptions of the Raman active modes of BaCIF and was able to assign
the bands unequivocally from a single crystal Raman study. Since the bismuth
oxide halides are isostructural with BaC1F it should be possible to give an

Table 2. Raman spectra of the bismuth oxide halides (values in cm -1)

BiOCl BiOBr BiO! Assignment

60 57 A]~
92 (1-5) Eg
146 (10.0) 113 (10.0) 85 (10-0) AI~
202 (2-3) 162 (0.8) 151 (3"7) Eo
400} 385 340} Big
410 Eg

The values m parenthesis indicate the relative peak heights of

bands recorded using the same slit settings (see experimental
section).

(o) (b)

540 340 40 540 340 40

crn-i cm-~

Fig. 2. Raman spectra (3 cm -1 slit width) of(a) BiOC1, (b) BiOBr run as powders.
1534 J. E. D. D A V I E S

assignment for the bismuth compounds from a comparison of their spectra with
the corresponding spectra of BaCIF and BaBrF.
The Raman bands in the 400 cm -1 region change very little in going from
BiOCI to BiOBr. Only one broad band is observed for the chloride and the iodide,
but two bands, at 410 and 385 cm -1, can be distinguished in the spectrum of
BiOBr and are assigned to the Eg and Big modes involving motion of the oxygen
atoms.
The Raman bands below 200 cm -1 are halogen sensitive and are assigned to
modes involving motion of the halogen atoms. Since symmetric vibrations usually
give rise to more intense Raman bands than asymmetric vibrations, the strong
bands observed at 146 cm -* for BLOC1, at 113 cm -1 for BiOBr, and at 85 cm -~
for BiOI are assigned to the A~g internal B i - X stretching mode. Similarly the
bands observed at 202 cm -1, 162 cm -~, and 151 cm -1 for the chloride, bromide
and iodide respectively are assigned to the Eg internal B i - X stretching mode.
Two external modes are expected of species Eg and Alg. Comparison of the
relative intensities of the BiOBr bands at 92 and 57 cm -~ suggests that the
former should be assigned to the Eg mode and the latter to the A~g mode. In
BiOC1 the Ey mode is probably masked by the strong band at 146 cm -1, whilst
the 60 cm -~ band is assigned to the A ~o mode. In BiOI both the Eg and A 1~ modes
probably give rise to Raman bands below 50 cm-k

EXPERIMENTAL
The compounds were obtained from two sources: commercially available samples and samples
prepared as described by Brauer [I 1]. Both sets o f samples gave similar spectra.

Infrared spectra
I.R. spectra in the range 600-200 cm -1 were obtained on a P E 225 spectrometer. The samples
were examined as nujol mulls between CsI plates. Spectra in the range 400-40 cm -1 were recorded
on a RIIC FS 720 interferometer. The samples were examined as nujol mulls on polythene plates.

Raman spectra
The Raman spectra were excited by means o f a C R L Model 52K krypton laser and recorded on a
Cary 81 spectrometer. The chloride and bromide were examined using the 5682 A line with a power
of 25 mW at the sample. The red iodide required the 6471 A line with a power of 50 mW at the
sample. All samples were examined as powers and the spectra were recorded using 3 cm -1 slit widths.
The spectrometer was calibrated using krypton emission lines.
Different slit settings were used in recording a spectrum. In recording the BiOBr spectrum shown
in Fig. 2, the region 40-70 cm -t used single slits, 2.5 cm slit length, the region 70-300 cm -~ used
single slits, 10 cm slit length, and the region from 300-540 cm -~ used double slits, 10 cm slit length.
It is only possible to compare relative intensities o f bands which have been recorded using the same
slit and slit length settings. There are, consequently, some bands in Table 2 which have no intensity
value.

Acknowledgement-I would like to thank Professor N. Sheppard, F.R.S., for the use of the R I I C
FS-720 at the University of East Anglia.

11. G. Brauer, Handbook of Preparative Inorganic Chemistry, Vol. 1, 2nd Edn. Academic Press,
London (1963),