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The crystal structure and absolute optical chirality of paratellurite, α-TeO2

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1988 J. Phys. C: Solid State Phys. 21 4611

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J. Phys. C: Solid State Phys. 21 (1988) 4611-4627. Printed in the UK

The crystal structure and absolute optical chirality of

paratellurite, a-TeO,

P A Thomas
Clarendon Laboratory, Parks Road, Oxford OX1 3PU, UK

Received 21 March 1988

Abstract. The crystal structure of paratellurite, cu-Te02, space group P4,2]2, U =

4.8082(3) A, c = 7.612(1) A, is refined from single-crystal x-ray data (547 unique
reflections). The atomic arrangement in the structure is correlated with the experimentally
observed optical rotation (OR) along the unique axis. A structural origin for the OR is
identified and demonstrated through the development of model structures. Calculations of
the OR and birefringence in @-Te02are made (using the program of Devarajan and Glazer)
and it is demonstrated that the explicit inclusion of the contribution of the lone pair of Te(IV)
to the optical response is essential for good agreement with experimental data.

1. Introduction

cu-Te02 is of technological importance because of its acousto-optic properties which

result from the coupling of its unusual elastic behaviour (Arlte and Schweppe 1968,
Uchida and Ohmachi 1969, Ohmachi and Uchida 1970) to its high birefringence
( A n = 0.1557 at 589.3 nm, Uchida (1971)). Large crystals of a-Te02are easily obtained
from the melt (Liebertz 1969) and device-quality material may be grown using weight-
controlled Czochralski techniques such as that of Silvestrova er a1 (1981). The optical
properties of the material that have been extensively studied include its linear electro-
optic behaviour (Ewbank and Newman 1982), its non-linear optic response (Okada er
a1 1977), and its optical absorption and reflection spectra (Takizawa 1980, 1981). The
large optical activity of cr-TeO, (106" mm-' at 589 nm, Uchida er a1 (1970)) has been the
subject of much investigation (Uchida 1971, Belyaev er a1 1976) particularly because of
its high dispersion with wavelength (the specific rotation varies from 587""-' at
370 nm to 37" mm-' at 900 nm). A recent study (Klimova er a1 1986) of the circular
dichroic absorption spectrum of the material has also been carried out.
Several previous studies of the crystal structure of cu-Te02 have been made. The
earliest attempt was by Goldschmidt (1931) who reported an ionic structure of rutile
type, space group P4/mmm(D&). Stehlik and Balak (1948) redetermined the structure
from single-crystal x-ray data and found that the c-parameter of the rutile-type cell
was doubled, leading to the assignment of space group P41212(Dj) or P4,2,2(D:).
Leciejewicz (1961) investigated the structure by neutron powder diffraction and con-
firmed the assignment of one of the latter space groups. He disagreed with Goldschmidt
about the nature of the compound, finding a degree of covalency indicated by the length
of the shortest Te-0 bonds in the highly distorted coordination polyhedron of tellurium.

0022-3719/88/254611 + 17 $02.50 @ 1988 IOP Publishing Ltd 4611

4612 P A Thomas

Lindqvist (1968) undertook the next study of single-crystal a-Te02 and refined the
structure from three-dimensional film data. A contemporary structural study by Kon-
dratink et a f (1987) has also very recently appeared and their data provide a good basis
for comparison with the present study.
This work is concerned with the correlation of the well documented optical activity
of a-TeO, and its crystal structure. Such a study necessitates the determination of the
absolute chirality of the crystal structure of the sample studied optically. Stadnicka et af
(1985), in their study of the structural chirality and optical activity of cu-LiI03, used a
limited data set and looked only at Bijvoet pair ratios in determining the absolute
chirality. However, at the time of commencement of this study, the crystal structure of
a-TeO, was not sufficiently well determined to allow the consideration of Bijvoet pairs
only. In addition, positive-definite anisotropic temperature factor matrices for both Te
and 0 were not known, an important omission because Glazer and Stadnicka (1986)
have shown that knowledge of the orientation of the thermal ellipsoids may be of use in
deducing the structural origin of optical activity. Also, for calculation of the optical
rotation and birefringence using the method of Devarajan and Glazer (1986), very
accurate structural parameters are required, as the calculations are sensitive to relatively
small shifts in the atomic coordinates. Therefore, a complete structural study of
single-crystal a-Te0, was undertaken.

2. Experimental details

A large Czochralski-grown crystal of Lu-TeO, was obtained from G E C (Hirst) Research

Centre. A (001) section of the crystal of thickness 0.29( tO.O1) mm was cut and polished
and examined between crossed polars. The section was of uniform colour, free from
domains and of high optical quality. A very good uniaxial figure (figure l(a)) was
obtained with a Bertrand lens in conoscopic observation. O n insertion of a quarter-wave
plate above the objective, a clear view of Airy’s spiral was obtained (figure l(6))

Figure 1. ( a ) Uniaxial conoscopic figure for a (001) section of a-TeO,. (b) Airy’s spiral for
dextro-rotatory a-Te02.
 Crystal structure of paratellurite 4613

demonstratingthat the crystal was dextro-rotatory.The same effect was seen at all points
on the slice, showing that the sample was uniformly of one chirality. Measurement of
the optical rotatory power at 632.8 nm using a standard laboratory microscope gave
p = 84( k3)" mm-' in agreement, to within the errors, with the results of Uchida (1971).
Many small cubes (of side = 0.3 mm) were cut from the (001) plate and ground in a
compressed-air spheriser in an attempt to produce spheres suitable for x-ray work with
this highly absorbing material. However, highly anisotropic ellipsoidal pieces always
resulted. Therefore, a small section (total measured volume 0.0041(~0.0004)mm3)
produced by slicing one of the cubes was used for the structure determination as detailed
below (table 1). At the end of the refinement, all parameters converged to A/cr < 5%.
The rather high peaks remaining in the difference map (Apmax = 3.55 e A-3) are not
unusual in compounds of Te(1V) (Lindqvist 1968, Swink and Carpenter 1966, Pic0 et a1
1986) and they were also commented upon by Kondratink and co-workers in their study
of cu-TeO2.They found that these peaks could be eliminated by allowing Te to vibrate
anharmonically.
The Hamilton significance test on the generalised R-factors for the two enantio-
morphic space groups showed that P41212could be chosen as the correct space group to
a significance level of better than 5%. In addition, Bijvoet pairs of reflections (hkl and

Table 1. Summary of the experimental conditions and refinement details.

Crystal colour, shape and size Colourless, trapezoidal prism, 0.169 mm

(base) x 0.144nm (height) x 0.175 mm
(thickness)
Diffractometer Enraf-Nonius CAD-4
Radiation Graphite monochromated MO K a
Scan mode and scan width w-26, (0.65 + 0.35 tan 6)'
Number of reflections and angular range 25, 6" < 9 < 22"
for obtaining lattice parameters
Lattice parameters measured a = 4.8082(3), c = 7.612(1) A
Maximum sin O / A 0.9044 A-'
Ranges of h , k , 1 &8, 0-8, -13-13
Intensity control Monitored hourly, variation < 1%
Number of reflections measured 1301 ( I > a ( 4 )
Number of unique observed reflections 547 ( F , > 2.5a(F0))
R internal on F 0.0399
Absorption correction Analytical ( S H E L X ~ ~ )
Maximum and minimum transmission 0.2082. 0.0974
factors
Model structure Te position from Patterson map, 0
position from difference synthesis (cf
model of Lindqvist (1968))
Atomic scattering factors, f ' and f " International Tables for X-ray
Crystallography (1974), neutral atoms
Refinement method Full-matrix least squares (SHELXX)
Reflections suppressed 93 low-angle extinction/absorption
affected, very weak high-angle
Number of parameters 19
Isotropic extinction parameter 0.028 x mm
R(wR), R~(p41212) 0.0244 (0.0213), 0.0284
R(wR), R G ( P ~ $ I ~ ) 0.0256 (0.0229), 0.0305
Weighting scheme l/(a2(F,) + gE),g < 0.0001
Final maximum residual electron density 3.55 e A-'
4614 P A Thomas

&kr>were considered and the theoretical ( A F : ) and observed ( A F : ) Bijvoet differences

(table 2) were compared for 26 pairs of reflections with IAFclz> 3%.
Agreement in sign between AC and AhFf was obtained for 22 reflections, but the
magnitudes were frequently quite different (cf Stadnicka er aZl985). Of the four pairs
of reflections for which A G and AhFf had opposite signs, one was a pair of high-angle7
weak reflections subject to poor counting statistics (1 5 10 and 5 10) and the other three
showed low calculated Bijvoet pair differences (-3%) and represent the level of the
fluctuations in the determination of absolute configuration from these data by this
technique. However, consideration of the Bijvoet pairs supported the assignment of the
space group P4,2,2. The final atomic coordinates and temperature factors are given in
table 3 and the important bond lengths and angles in table 4.
The structural coordinates for both Te and 0 obtained from this study are in excellent
agreement with those of Kondratink et a1 (1987) and those determined from high-
resolution powder diffraction (Thomas 1987). Atoms 0 1 , 0 5 , 0 2 ’ , 0 8 , 0 6 ’ , 0 3 ‘ form
a highly distorted octahedron (not joined in figure 2) around the tellurium atom Te(1).
This coordination polyhedron is more distorted than that found previously, with the
equatorial and axial Te-0 bonds being more different from each other than before

Table 2. Bijvoet pair differences calculated by

for reflections sensitive to anomalous scattering.

hkl F?(hkl) P(hkl) Ae(%) AE(%)

147 1183 1018 +4.8 +14.9
242 466 408 +6.9 +13.3
234 335 357 -7.8 -6.3
246 299 269 +5.9 +10.6
154 3091 2652 +4.8 +15.3
343 1576 1592 +4.1 -1.0
274 299 278 +7.1 +7.3
164 123 112 -7.4 +9.4
149 707 734 -5.3 -3.7
183 1232 1142 +3.6 +7.0
141 2591 2381 +3.5 +8.4
129 454 424 +3.8 +4.5
262 404 416 -3.1 -2.9
344 552 595 -5.1 -7.5
362 795 772 +4.4 +2.9
3411 552 586 -4.2 -6.0
371 1289 1296 +3.8 -0.5
562 250 260 -6.1 -4.7
364 615 586 +4.9 +4.8
374 282 310 -4.5 -9.5
474 67 1 729 -5.8 -8.3
355 1115 1197 -5.9 -7.1
255 1689 1568 +5.1 +7.4
165 1505 1436 +5.3 +4.7
566 207 218 -4.0 -5.2
254 353 350 -3.3 +0.8
1510 34 32 -7.0 +6.1
 Crystal structure of paratellurite 4615

Table 3. Structural and thermal parameters for cu-TeOz.The units of U , are A’.
W x , x, 0 ) x = 0.0268(0)
U11 = U22 = 0.0069(1)
U33 = 0.0086(1)
U , = -U3, = -0.oO01(0)
U I 2= -0.0013(1)
O(x, y , z ) x = 0.1386(4)
y = 0.2576(5)
z = 0.1862(2)
U11 = 0.0113(7)
U,, = 0.0129(6)
U33 = 0.0119(5)
U , = -0.0053(5)
U,, = -0.0017(4)
U,* = -0.0043(6)

(cf A = 0.244 A with Lindqvist A = 0.18 A). This indicates a trend towards twofold
coordination of tellurium by oxygen (cf Brown 1974), with the Te(1)-O(1) and Te(1)-
O(2) bonds accounting for more than 60% of the valence distribution of the Te atom. The
short (1.878 A) Te-0 bond length suggests covalent bonding typical for low coordination
numbers and is shorter than the ‘theoretical’ (1.906 A) bond length expected for typical

Table 4. Important bond lengths and angles in cu-TeOz (refer to figure 2 for labelling).

Bond Length (A)

Tel-Te2 3.743(2)
Tel-01 = Tel-05 1.878(1)
Tel-02’ = Tel-08’ 2.122(1)
Tel-06’ = Tel-03‘ 2.866(2)
01-05 = 03-06’ 2.945(2)
01-08‘ = 0 5 - 0 2 ’ 2.791( 1)
Intra-helix bond:
0 1 - 4 = 01-02’ 2.688(1)
01-06’ = 0 5 - 0 3 ’ 2.865( 2)

Bond Angle (deg)

Linking angle for TeOz units:

Tel-01-Te3 138.67
Te 1-0 1-Te2 156.13
Octahedral angles (TeO, coordination
polyhedron):
01-Tel-05 103.30
01-Tel-02‘ 84.24
01-Tel-08’ 88.30
01-Te 1-03’ 172.10
01-Tel-06’ 70.85
02’-Te 1-08’ 167.97
02‘-Tel-03’ 90.06
02’-Tel-06’ 96.36
4616 P A Thomas
0 0

0
0

Figure 2. A schematic diagram of the w T e O , structure with identification of atoms

particularly relevant to the coordination of tellurium (see table 3) and the structural origin
of optical rotation. The maximum 0-0 bond length is 3.2 A .

trigonal bipyrimidal fourfold coordination of tellurium by oxygen (Philippot 1981). The

axial Te-0 bond length (2.122 A) exceeds the expected theoretical value (2.02 A)
pointing again to a coordination number closer to 2 than 4.The sublimation behaviour
reported by Prescher and Schroedter (1962) is also consistent with the treatment of
the TeO, unit as a structural entity, and further demonstrates a degree of molecular
character. Both Te and 0 atoms showed significant anisotropy in their thermal motions
(figure 3).

0
Figure 3. Thermal ellipsoids for the tellurium and oxygen atoms in a-TeO, plotted at the
70% probability level. The maximum Te-0 and 0-0 bond lengths are 2.7 and 2 . 8 A
respectively.
 Crystal structure of paratellurite 4617

3. The structural origin of optical rotation in cu-Te02

The structural study conclusively showed that the atomic arrangement described by
space group P4,2,2 corresponded to optically dextro-rotatory a-TeO,. A correlation
between the observed optical rotation and the known atomic arrangement was then
sought in a similar way to that of Glazer and Stadnicka (1986) (hereafter referred to as
GS). It was assumed that the oxygen atoms were very much the more polarisable species
(compared with the high-valence ‘cation’ Te4+)and therefore that they were the more
significant contributors to the optical rotation (OR). This suggested that an effective helix
of oxygen atoms should be found. For a helix to be ‘effective’, the orientation of the
anisotropic polarisability ellipsoids should be either tangential or radial to the helix cross
section, as these extremes were previously identified (by GS) as the configurations that
produce rotation of the plane of polarisation of incoming light respectively with or
against the sense of the helix.
In the a-Te02 structure, four perfectly regular helices of oxygen atoms appear
(figure 4) described by the 41 screw axis element of the space group. The 0-0 bond
length in helices 1 4 i.e. the intra-helix bond length is 2.688 A (e.g. 01-02’ = 01-04)
which should be compared with the inter-helix bond lengths 01-08 (2.791 A), 01-06’
(2.865 A) and 0 1 - 0 5 (2.945 A). Therefore, it was expected that the anisotropy of the
polarisability ellipsoid of, for example, 01 on helix 1, should be influenced by several
of its neighbours in a rather complex way. In order to determine the ‘exact’ orientation
of the anisotropic polarisability ellipsoids, the program of Devarajan and Glazer (1986),
hereafter DG, was used. The average refractive index, 2.31 at 6328 A, was calculated
from the data of Uchida (1971), and the Clausius-Mossotti relationship was used to
calculate the total polarisability volume (24.08 A3) in the unit cell. A disappointing
quantitative fit to the experimental data (no= 2.2597, ne = 2.4119, p = 86.9”mm-’) was

Figure 4. Polarisability ellipsoids for the oxygen atoms (calculated using the program of DG)
for input polarisability volumes aTe= 0.02 A’ and . a = 2.68 A3. The calculated OR and
refractive indices corresponding to the figure are 98” mm-I, 2.062 and 2.118. The heights of
the oxygen atoms are given as -100 z/c. The maximum 0-0 bonding distance is 3.2 A . 6
marks the original angle between the cell edge and the line joining the helix axis and oxygen
atom E.
4618 P A Thomas

obtained, although the sign of the calculated OR was in agreement with observation. It
was found that the calculated OR was always too high (e.g. 188" mm-') at polarisability
values (aTe= 0.02 A3,a. = 3.00 A3)suchthat the refractive indices were approximately
correct (no= 2.2752, ne = 2.3554). The calculated birefringence was always significantly
lower than the very large experimental value (0.1522). A value of 98" mm-' for the OR
was obtained for aTe= 0.02 A3 and a. = 2.68 A3 when lower values of the refractive
indices were accepted.
The structural origin of the optical rotation may be deduced from consideration of
the polarisability ellipsoids calculated for the oxygen atoms (figure4). These were found
to lie neither substantially tangential nor radial to the helices 1 to 4 and were not closely
orthogonal to the thermal ellipsoids (in contrast to the findings of GS). These individual
helices were discounted as the structural features of influence in producing OR. Close
examination of the a - T e 0 2 structure revealed another helical arrangement of atoms
(helix a, figure 4 and table 5) resulting from bonding interactions between atoms from
each of the four helices 1-4. All of the eight oxygen atoms in the unit cell lie either on
helix a or helix b which are identical geometrically (equal pitch and equal intra-helix
bond lengths) and therefore contribute equally to the OR. The calculated polarisability
ellipsoids of the oxygen atoms lie very closely radial to these right-hand screw helices
(RS1/4 in the terminology of GS) which have the same sense as helices 1-4. The radial
orientation of the ellipsoids predicts (after GS) a contribution of the OR in the opposite
sense to that of the structural helix, i.e. a dextro-rotatory contribution, in agreement
with observation.
The prominent geometrical characteristic of helices a and b is their very small cross
sectional area when viewed along the c axis resulting from the 'steepness' of the pair of
bonds 04-08 and 0 7 - 0 2 (tending to be parallel with [Ool]) and the flatness of the
remaining pair of bonds (tending to be parallel with the (001) plane). The influence of
such a helix on an incoming plane wavefront tends to be smaller than that of a helix of
greater cross sectional area (i.e. of greater spatial extent perpendicular to the propa-
gation direction). In the a-TeO, structure, there also exists a much larger structural
helix of atoms (helix c, see figure 4 and table 5) i.e. the encircling figure IJKLMNOPQG
extending outside the unit cell, consisting entirely of inter-helix 0-0 bonds and again
involving all of the eight oxygen atoms of the unit cell. This helix (albeit imperfect) has

Table 5. Classification of helices important to the calculated OR in the real a-TeO, structure
and the model (i) structure (negative extreme).
~~

Contribution
Helix Figure Atoms Sense of Orientation to optical
label for reference in helix helix of ellipsoids rotation

a 4 ABCD Right-hand screw Radial Dextro-rotatory

b 4 EFGH Right-hand screw Radial Dextro-rotatory
C 4 IJKLMNOPOG Left-hand screw Tangential Dextro-rotatory
It 4 BJRE Right-hand screw Neither radial Zero
nor tangential
d 7(b) ABCDEFGH Right-hand screw Tangential Laevo-rotatory
e 7(b) BJFI Left-hand screw Tangential Dextro-rotatory
It 7(b) AJGH Right-hand screw Tangential Laevo-rotatory

t Also applies to helices 2 , 3 and 4.

 Crystal structure of paratellurite 4619

the character of a left-hand screw and, furthermore, the polarisability ellipsoids lie
approximately tangential to it. Therefore, the sense of the contribution of this structural
helix to the OR is also dextro-rotatory. Thus it is likely that the dextro-rotatory effects of
the two types of closely inter-linked helices combine in producing the high optical activity
of a - T e 0 2 .
It is evident that the OR in this material, with its relatively small unit cell and
its structure intermediate between molecular and framework oxides, is governed by
oxygen-oxygen interactions on a large scale. The helices 1 4 , initially expected to be
prominent contributors to the OR, are made ineffective because of the influence of inter-
helix interactions on the anisotropy of the polarisability ellipsoids. To test the effect of
these interactions, calculations were carried out on various model structures. The two
types of model structure were developed from the real a - T e 0 2 structure as follows.
(i) The relative orientations of helices 1 4 were varied by rotating the oxygen
coordinates anticlockwise about the helix axes.
(ii) The helices 1-4 were gradually separated by expanding the unit cell.
In both models the nature of the individual helices 1 4was preserved, i.e. the length
of the intra-helix bonds was maintained at 2.688 8, (helix cross section constant) and
the z-coordinates of the oxygen atoms were unchanged (helix pitch constant). New
coordinates for the 0 atoms were generated within spacegroup P41212so that the
symmetryofthestructurewaspreserved. Calculationswerecarriedoutfor aTe= 0.02 A3
(the Te contribution at an unchanged position is virtually negligible) and a. = 2.68 A3
giving pcalc= 98" mm-' for the real structure. It is clear from the results of these cal-
culations (figure 5(a) and ( b ) )that the calculated OR (pcalc)
is very sensitive to small shifts
in atomic coordinates (emphasising the importance of obtaining good structural data).
It is also evident, particularly from model (i) that the calculated OR is, as expected,
strongly dependent upon the relative orientations of these elements and the interaction
between them. It is instructive to compare the three cases.
(i) Positive optical rotation (pcalc= 98" mm-'), rp = 0" (real structure, figure 4)
(ii) Zero optical rotation (pcalc= 0" mm-'), rp = 14.5" (figure 6(a)).
(iii) Negative optical rotation (pcalc= -208" mm-', = 30" (figure 6 ( b ) ) .

The model (i) structure for pcalc= 0" appears more open and expanded along [110]
than the real structure because inter-helix bonds of type 01-06' joined in figure 4 are
no longer joined in figure 6(a). Inter-helix bonds of type 01-08 are joined in both
figures. During the modelling process, the important inter-helix bond lengths show
different variations (figure 7 ( a ) , ( b )and (c)).
It is clear that the influence of the neighbouring oxygen atoms on a single oxygen
atom is dramatically altered, leading to a significant change in the calculated OR. The
results of the calculations for the two types of model structure can be explained in terms
of the influence of inter-helix interactions as follows.
(i) As the helices are rotated, the 01-06' bonds lengthen and the effects of the three
helices (i.e. a, b and c) involving this bond are weakened, leading to a decrease in
calculated OR. The configuration of the polarisability ellipsoids with respect to helices
1-4 does not change dramatically and they continue to make no contribution individually
to the OR. At the pcalc = 0" position, with the 01-06' bond length at 3.52 A,it appears
that the large LS helix (c) and the RS helices (a and b) are effectively 'broken down' and
cease to influence the OR. However, there are no other effective helical features in the
4620 P A Thomas

-'2
-180 6 12 18

Angie of helix rotation Ueg)

24

1
z
L 451
_ a -
I

1
Cdl expanson f o c t a

Figure 5 . (a) Graph showing the variation of the calculated optical rotation with the helix
rotation angle q (indicated o n figures 6(a) and ( b ) ) .( b )Graph showing the variation of the
calculated optical rotation with the cell expansion factor multiplying the a and b dimensions
of the unit cell.

model structure at this point and therefore a calculated OR of zero is obtained from a
structure that in theory, from symmetry considerations, could show a non-zero effect (a
situation often found with naturally occurring materials). As helix rotation is continued
beyond this point, a negative calculated OR appears and grows quite rapidly. This occurs
because the helices 1-4 finally have an influence on the OR as the highly anisotropic
polarisability ellipsoids begin to turn tangential to them (figure 6 ( b ) ) .The large laevo-
rotatory effect of these perfectly regular symmetric structural helices consisting of short
0-0 bonds (length 2.688 A) is compounded by the steadily growinginfluence of another
structural feature (helix d, see figure 6 ( b )and table 4) which takes on a helical nature as
a result of the shortening of the 01-08' bond (2.597 8,at this negative extreme). Helix
d, to which the polarisability ellipsoids lie closely tangential, is imperfect in a similar way
 Crystal structure of paratellurite 4621

to the large dextro-rotatory helix c of the true structure. Again in direct geometrical
analogy with helix a of the true structure, helix e (which is described in the opposite
sense to a) appears as a result of the severe shortening of the bond 01-06. However,
the tangential orientation of the ellipsoids to this helix predicts a dextro-rotatory con-
tribution, but this is clearly superceded by those helices in the structure giving laevo-
rotation, and to so great an extent that the magnitude of the calculated OR at the negative
extreme exceeds the positive OR of the real structure. This disparity reflects the shorter
bond lengths and greater regularity of the effective helices 1-4 in the model structure
compared with the rather irregular features present in the true structure. The calculated
anisotropy of the polarisability ellipsoids involved in the contributing helices is also much
greater at the negative extreme and the OR depends critically on this (Ramachandran
1951 and cs).

Figure 6. ( a ) Polarisability ellipsoids plotted for the oxygen atoms for the model 1 structure
(p = 14.S0)givingp,,,, = 0" mm-l.Themaximum0-Obondlengthis3.2 A.Thescalefactor
for the ellipsoids is 0.035. ( b ) Polarisability ellipsoids plotted for the oxygen atoms for the
model 1 structure (p = 30") giving pcaic = -208 mm-' (negative extreme). The maximum
0-0 bond length is 3.2 A. The scale factor for the ellipsoids is 0.035.

(ii) As the helices 1-4 are pulled apart via expansion of the unit cell, the lengths of
all inter-helix bonds are increased. Gradually then, the inter-helix bonds linking the
helices a, b and c are 'broken' so they become ineffective from the point of view of OR.
The helices 1-4 become steadily more independent of each other and provide a laevo-
rotatory contribution (as the polarisability ellipsoids take up a more tangential orien-
tation) which eventually supercedes (at cell expansion 1.25) the very much diluted
dextro-rotatory contribution from the original helices. At large cell expansions (>1.3),
the incoming light 'sees' only the laevo-rotation produced by a 4, helix of oxygen atoms
as if in isolation. Hence, the calculated OR levels out at the small negative value of about
-6" mm-'. At the pcalc= 0" mm-' point, the bond lengths 01-08 and 01-06' have
values of 3.563 and 3.676 8, respectively. These should be compared with the 01-06'
bond length of 3.52 A at which pcalc= 0" mm-' as a result of helix rotation. Together,
the results suggest that the maximum 0-0 bond length within an effective helix able to
influence the OR lies in the region 3.5-3.7 A.
4622 P A Thomas

!I
4 2.60
z

2.50 * * * . I
*.
=*..* 1

$ 1
n
* * I
2.93
1 * * .

. t . f ' , , , , , ,
 Crystal structure of paratellurite 4623

4. Quantitative fitting of the optical properties of a-Te02:the influence of the lone pair

The structural origin of the large OR in a-TeO, has now been identified. However, the
extent to which the experimental data for the birefringence and OR of a - T e 0 2have been
fitted using the program of DG is disappointing. There are particular errors involved in
using the point-dipole approximation to describe a - T e 0 2because there is a high degree
of covalency in some Te-0 bonds (in contrast with the assumed ionic extreme) and also
because the bonding environment of Te deviates very much from being spherically
symmetric (Reijnhart 1970). In the foregoing treatment, the contribution of Te to the
optical properties of the material has been considered to be virtually negligible in
comparison with that of the oxygen atoms (as G S found for similar systems). Therefore,
it would seem that errors in the representation of the anisotropic polarisability of the
tellurium atom should have only a small importance in as much as they influence the
polarisability of the oxygen atoms. For input polarisability volumes aT,= 0.02 A3 and
a = 2.68 A3 the level of influence is indeed almost negligible. However, the Te atom
.
(Te(1V)) has the ‘inert pair’ valence state in this compound and, because of the lone
pair, is relatively more polarisable than other high-valence metal cations (Orgel 1959).
This suggests that the above polarisability volume for Te is too small, but simply
increasing the ‘free atom’ isotropic input polarisability only worsens the results of the
calculations. The presence of the lone pair also causes the electronic distribution of
Te(1V) to be highly aspherical and this effect is not accounted for by calculation of the
effective anisotropic polarisability ellipsoid from consideration of the bonding environ-
ment (i.e. the dipole-dipole interactions betweenneighbouringatoms).It issubstantially
incorrect to approximate the polarisability ellipsoid of the tellurium atom to a sphere.
A significant improvement can be obtained by incorporating the lone pair as a separate
entity (E) situated closely adjacent to the tellurium atom and able to respond inde-
pendently to the propagating electric field. The approach finds comparison with that of
Okada et af (1977) (after Bergman and Crane 1974) when calculating the non-linear
polarisability of a Te-0 bond from their experimental data. They assumed that the
lone pair made a separate contribution to the non-linear optic response, its non-linear
polarisability being approximately equal to the bond polarisability of a short (1.9 A) Te-
0 bond. Using their constraint on the direction cosines of the ‘bond’ linking Te and E,
i.e. that the ‘bond’ should lie parallel to the long Te-0 bondingdirections and antiparallel
to the short bonding directions, the lone pair is located on the [110] axis on the opposite
side of the origin to Te( 1). This is consistent with the calculation of the lone-pair position
using the method of Galy et af (1973), in which the lone pair is considered to occupy an
otherwise vacant vertex of the Te(1V) coordination polyhedron (in this case, the third
equatorial position of a trigonal bipyramid). Then the resultant arrangement of Es and
oxygen atoms in the structure is typical of the hexagonal close-packing of anions found
in comparable structures for which the cation does not have the inert-pair valence state.
With our structural data, the lone-pair position was fixed at (-0.173, -0.173,O)
giving a Te-E distance of 1.38 A. The calculation of OR and refractive indices of a-TeO,
was repeated with the lone pair initially assigned a small polarisability volume at the
above coordinates. Finally the best fit no = 2.3098, ne = 2.4111 ( A n = O.lOl>, p =
86.72” mm-I was obtained for the input polarisability volumes aTe= 0.332, aE = 0.554
and a,,= 2.602 A3.
4624 P A Thomas

5. Discussion

The polarisability volume assigned to the lone pair is quite high. However, if only valence
electrons are considered to have significant polarisability, the non-bonded electrons (i.e.
the lone pair) are certainly more 'free' to respond to the propagating field than electrons
involved in short Te-0 bonds. Hence aEmay be greater than aTe. The calculated values
obtained for neand p are in very good agreement with the observed values, but the value
for no is too high, leading to a low calculated birefringence that is impossible to correct
without degrading the fits of the other parameters. Thus, the point-dipole approximation
is unable to account completely for the large optical anisotropy (An = 0.15) displayed
by this material.
The important physical effect of the explicit inclusion of the lone pair is clearly
demonstrated (figure 8(a) and ( b ) ) .With its inclusion, the component of the anisotropic
polarisability simultaneously tangential to the large encircling helix c identified pre-
viously and radial to helices a and b is smaller than when it is omitted. The oxygen
polarisability ellipsoids are less anisotropic (confirmed numerically from consideration
of the diagonalised polarisability tensors) so the effect of the helices contributing to
dextro-rotation diminished and the OR is decreased to give results in better agreement
with experiment. The splitting of the total polarisability contribution of Te (now rela-
tively large for a metal cation at 0.866 A3) over two sites (atom lone pair) has a +
pronounced effect on the oxygen polarisability ellipsoids, and the same effect cannot be
obtained if the total polarisability is located at either of the sites alone (results very far
from the experimental values are obtained).
The inclusion of the lone-pair contribution in the calculation necessitates the intro-
duction of further parameters to the input model, i.e. the coordinates of the lone-pair

lbl
la I

Figure 8. ( a ) The configuration of the polarisability ellipsoids of the oxygen atoms with
respect to the helices of importance to the OR when the lone pair is included (aE= 0.544,
aTe= 0.332 and rro = 2.602 A3). This figure corresponds to the final calculated OR of
86.72' mm-l. The maximum 0-0bond length is 3.2 A and the scale for the ellipsoids is
0.035.( b )The polarisability ellipsoids for the oxygen atoms when the lone pair is not included
(all other parameters are as figure 8(a) for the purposes of comparison). The calculated OR
corresponding to this figure is too high because the lowering effect of the lone pairs is absent.
 Crystal structure of paratellurite 4625

site and the independently variable lone-pair polarisability ,aE.The coordinates have not
thus far been considered as variables-instead they have been fixed using stereochemical
considerations only. Whether or not the chosen position for the lone pair is the best can
only be ascertained by allowing the systematic variation of the coordinates. For example,
important and informative variations include:
(i) the movement of the site along [110] to test the effect of different Te-E ‘bonding’
distances ;
(ii) the movement of the site slightly out of the x y plane ( z # 0) thereby removing
the restrictions that twofold symmetry places on the anisotropic polarisability ellipsoid.
Small changes only of types (i) and (ii) affect the calculations significantly and suggest
that a ‘best’ position for the lone pair could be found. However, the polarisabilities cu,,,
and CY, have also to be adjusted to attain the best fit to the datain any such calculation.
Further studies in compounds of Te(1V) are necessary in order to gain greater insight
into the significance of the lone pair to the optical properties of these materials.

6. Optical rotatory dispersion of a - T e 0 2

The optical rotatory dispersion (ORD) was calculated by scaling the initial input polaris-
ability values using Uchida’s refractive index data for different wavelengths in the
Clausius-Mosotti equation and then repeating the DG calculation. As expected, this
gave a better fit to the experimental data (figure 9) for intermediate-long wavelengths
(500-800 nm) than for short wavelengths because of the increasing influence at

r &OO

f
q-
I! ,001

e
250
4

-4

1
4ooo
I
5000 6000
1
7000
1
Wavelength of light (A,
Figure9.The observed (+) (afteruchida 1971)and calculated (*) optical rotatory dispersion
curves for cy-TeO,.
4626 P A Thomas

A < 500 nm of the strong absorption band at 240-300 nm (centre of gravity 2650 nm)
which causes the breakdown of the essential assumption that the crystal should be non-
absorbing. Additionally, the initial polarisability values were chosen for the wavelength
632.8 nm and therefore the errors inherent in the approximation of cu-TeOZto an ideally
ionic material were minimised at this point. Thus the very good agreement of the
experimental and observed data over a 300 nm range using only three variables (the
scaled input polarisabilities) is encouraging. However, as expected, better fits to the
observed dispersion across the whole wavelength range have been obtained using a
Drude-type two-oscillator model (Uchida 1971) and the modified oscillator formula
(proposed by Agranovich 1960) representing molecular and crystalline contributions to
the OR (Belyaev et af 1976) which take account of the influence of the short-wavelength
absorption resonances. Interestingly, Belyaev and co-workers found that the molecular
and crystalline contributions to the dispersion were approximately equal, suggesting a
tendency towards the covalent influence already discussed in this work.

7. Conclusions

The absolute chirality of the crystal structure corresponding to optically dextro-rotatory

cu-TeOzhas been determined. Qualitative anisotropic polarisability theory (as inter-
preted by GS) has been successfully used to find a structural origin for the high optical
rotation displayed by the material. Far from being a simple case determined by symmetric
structural helices described by space group symmetry, the OR has been shown to arise
through a complex system of oxygen-oxygen bonding interactions on the scale of the
whole unit cell. The vital importance of these interactions has been demonstrated by the
use of model structures and the interpretation of these results within a ‘helix theory’ of
optical activity gives further support to this view of the structural origin of OR.
Quantitative calculations of the birefringence and OR of cu-Te02have been carried
out using the purely ionic point-dipole approximation for a material which has significant
tendencies towards covalent character. Results in good agreement with experiment have
been obtained only by the explicit inclusion of the lone pair of Te(1V) as a polarisable
species at coordinates fixed by stereochemistry. The important physical effect of its
inclusion upon the response of the oxygen atoms to the propagating field has been shown
and again interpreted within the general theory of the correlation between OR and crystal
structure. The success of calculating the optical properties of cu-TeOzover a wide range
of wavelengths using this model provides encouragement for further studies on related
systems, particularly those in which a cation has the lone-pair valence state.

Acknowledgments
The author would like to thank J James of GEC (Hirst) Research Centre for providing
the crystal, Dr K M Stadnicka for collecting the x-ray data and Dr A M Glazer for advice
and discussions. Thanks are also due to the SERC for the grant that supported this work.

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