Spectrochimica Acta, Vol. 39A, No. 6, pp. 529-531, 1983 0584-8539/83 $3.00 + .

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Printed in Great Britain. © 1983 Pergamon Press Ltd.

The Raman spectrum of POCI3 in the solid state

S. R. G u m ^ and A. V. R. WARRIER
Solid State Physics Laboratory, Lucknow Road, Delhi-110007,India

(Received 18 Octobe, 1982)

Abstract--The Raman spectrum of POCI3 in the solid state has been recorded. The spectrum shows two
components for the non-degenerate v2 (A1)and v3 (A1)modes.This, together with the absenceof splitting of
the other modes suggests that the possible unit cell for the solid is cubic with four moleculesin the unit cell.

1. INTRODUCTION
POCI3 is a liquid at room temperature and freezes at
2°C. [1]. Its molecular structure has been established
by electron diffraction and microwave spectroscopy
and is shown to belong to C3o symmetry [2]. However,
there is no mention in the literature of its crystal
structure. The Raman and infrared spectra in the liquid
state have been reported [3] and the six observed
vibrational frequencies have been assigned on the basis
of C3o symmetry.
The Raman spectrum of many molecular crystals
have been used for establishing their crystal struc-
ture [4]. There appear to be no data on the Raman
spectrum of POC13 in the solid state.
2. EXPERIMENTAL
The Raman spectrum was recorded using the 4880 A
line of a Spectra Physics Model-165 Argon ion laser at
200 mW and a Model-700 Raman Spectrometer. The
detector was an I T T - F W 130 photomultiplier in the
photon counting mode.
Since POC13 dissociates in air, the liquid was loaded
into a conventional liquid sample cell of 0.5 ml ca-
pacity and sealed before recording the spectrum. For
recording the spectrum in the solid state, the sealed
sample cell was mounted on a copper block for good
thermal contact with proper openings at right angles
for allowing the laser beam to fall on the sample and
for collecting the scattered radiation. This block was
attached to the cold head of an Air Products CSA-202
closed cycle cooling system. The vacuum shroud was
fitted with fused quartz windows. The spectrum was
recorded at various temperatures below the freezing
point in order to see if there is any change in the
spectrum with temperature.
3. RESULTSAND DISCUSSION
POCI3 molecule has C3v symmetry and its nine
vibrational degrees of freedom are distributed as 3A 1
+ 3E. These are i.r. as well as Raman active and thus
one would expect six Raman lines. In Fig. 1 one can see
six Raman lines at 486, 1296, 267, 584, 337 and
193 cm-1 for POCI3 liquid. These modes are de-
signated as vl (A0, v2 (A0, v3 (A0, v4 (E), v5 (E) and
v6(E) respectively following earlier results[3]. Of
these, only in v2 and v3 modes is motion of oxygen
involved. In other modes, oxygen can be considered as
practically at rest.
Figure 2 shows the Raman spectrum of POCI 3
condensed into a solid. The most interesting thing to
observe is that v2 and v3 show a doublet structure while
the other modes remain the same as in the liquid state
with about the same relative intensities.
When the molecules are condensed into solid state,
the following can happen:
(a) All the modes show a shift in frequency. This can
be expected due to the increased interaction between
the molecules in the condensed state.
(b) Corresponding to each mode in the free state
more than one line can appear. This could be either due
to correlation splitting coming about due to the
presence of more than one molecule in the unit cell and
thereby introducing a coupling of the vibrations or due
to lowering of symmetry [5]. In the latter, only the
degenerate modes show splitting whereas the corre-
lation splitting can come about in the case of non-
degenerate modes as well.
In the spectrum (Fig. 2) in the condensed state only
non-degenerate modes v2 and v3 show a doublet
structure. The v2 mode shows two lines at 1294 and
1273 cm-~ and v3 mode shows lines at 276 and
265 cm- ~ respectively. This indicates that the unit cell
contains more than one molecule. Also since the
doubly degenerate modes v4, v5 and v6 do not show any
splitting, the molecular symmetry is not lowered. This
is possible only if the unit cell is having at least a three-
fold axis of symmetry, thus limiting the unit cell to
trigonal, hexagonal or cubic [6].
It can be seen from the spectrum that the lines which
show splitting are those in which motion of oxygen is
involved. This leads us to conclude that the interaction
between the molecules in the unit cell is through the
oxygen atoms in the neighbouring POC13 molecules.
This suggests that the possible orientation of the
POCI 3 molecules is that in which the oxygen atoms
point towards each other, so that only modes as-
sociated with the motion of oxygen are affected.
The following possible structures can be considered

529
 530 S.R. GUP"rAand A. V. R. WARRIER

-4,

N
m
l

I I l | I I ! I

1320 1250 600 500 400 300 200 150

WAVE NUMBER

Fig. 1. Raman spectrum of POCI 3 in liquid state (slit width 8 era- 1).

a
1320 12)50 6 0' 0 5 0' 0 4'0 0 3 '0 0 '
200 '
150

WAVE N U M B E R

Fig. 2. Raman spectrum of POC1 s in solid state (slit width 8 cm- 1).

in which the three-fold axis of the molecule is retained
and oxygen atoms point towards each other.
(a) A cubic unit cell with Td symmetry in which four
P O C I 3 molecules are packed such that the three-fold
axis of these molecules are along the apices of the
tetrahedron. In this structure all the oxygen atoms are
nearest to each other and they can interact strongly.
(b) A hexagonal or a trigonal unit Cell with two
POCIa molecules such that the three-fold axis of the
molecule coincides with the principal axis of symmetry
of the crystal and that the oxygen atoms of the two
molecules face each other.
In the cubic unit cell since there are four molecules in
the unit cell, one would have expected four com-
ponents for v2 and v3. However, because of the T d
symmetry o f the unit cell the four-fold degeneracy of v2
and va is split into a singly and triply degenerate mode,
thereby giving a doublet structure for the v2 and v a
modes.
If, on the other hand, a trigonal or a hexagonal
structure is assumed for the unit cell, because of the
presence of two molecules in the unit cell, the v2 and v a
modes split into two in which relative motion of the
oxygen atoms in the two molecules become symmetric
and anti-symmetric. This can lead to different in-
tensities for the split components, whereas in the cubic
structure in which the mode splits into A and T2, the
intensities can be nearly equal. In our spectrum, the
lines are nearly equal in intensity. This supports a cubic
structure for the unit cell. Thus from the observed
Raman spectrum, we are able to fix unit cell of POCI a
to cubic with Ta symmetry.
 Raman spectrum of POCI 3
4. CONCLUSIONS
T h e R a m a n spectrum of P O C I 3 in the solid state
shows splitting of v 2 a n d v 3 modes. This has been
interpreted as due to the presence o f more t h a n one
molecule in the unit cell. T h e absence o f any splitting of
degenerate m o d e s a n d the equal intensity of the two
c o m p o n e n t s o f v 2 a n d v a show a cubic structure with T d
symmetry a n d four molecules in the unit cell as a
possible crystal structure.
Acknowledgements--We are grateful to Drs T. Rs. R EDDYand
ABHAfor fruitful discussions and to the Director, Solid State
Physics Laboratory, Delhi for permission to publish this
paper.
531
REFERENCES
[1] C.R.C. Handbook of Chemistry and Physics, 60th edn.
(1979).
[2] K. NAKAMOTO, Infrared Spectra of Inorganic and
Coordination Compounds, 2rid edn, pp. 78-148.
Wiley-Interscience, New York (1970).
[3] T. MORITAN1, K. KUCmTSU and Y. MORINO, Inorg.
Chem. 10, 344 (1971).
[4] R. SOVlE, in Raman Effect, Vol. 2, pp. 759-810 (edited by
A. ANDERSON). Marcel Dekker, New York (1973).
[5] S.S. M1TRA,in Optical Properties of Solids, pp. 333451
(edited by S. N UDELMANand S. S. MITRA).Plenum Press,
New York (1969).
[6] International Tables for X-ray Crystallography, Vol. 1
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