Structure and hydrogen ordering in ices VI, VII, and VIII by neutron powder diffraction

W. F. Kuhs, J. L. Finney, C. Vettier, and D. V. Bliss

Citation: The Journal of Chemical Physics 81, 3612 (1984); doi: 10.1063/1.448109
View online: http://dx.doi.org/10.1063/1.448109
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 Structure and hydrogen ordering in ices VI, VII, and VIII by
neutron powder diffraction
w. F. Kuhs
Institut Laue-Langevin I56X; 38042 Grenoble, France
J. L. Finney
Department of Crystallography, Birkbeck College, University ofLondon, Malet Street, London WCI E7HX;
England
C. Vettier
Institut Laue-Langevin, I56X; 38042 Grenoble, France
D. V. Bliss
Department of Crystallography, Birkbeck Col/ege, University ofLondon, Malet Street, London WCI E7HX;
England

(Received 1 March 1984; accepted 15 June 1984)

The structures of deuterated ices VI, VII, and VIII have been studied under their conditions of
stability by neutron powder diffraction. The mode of ordering of (tetragonal) ice VIII is clearly
established, and no evidence is found of partial ordering as the temperature is raised. Ice VII is
accurately cubic with D 20 molecules disordered around their center of mass; there is no evidence
of partial ordering at any temperature. The water molecule geometry is normal in both phases,
and the hydrogen-bonded first neighbor in ice VIII is confirmed to be more distant than the first
nonbonded neighbor. The transition temperature between the two phases occurs at 263 ± 2 K,
some 11 K lower than expected. Hydrogen bond lengths in both phases are equal at the transition.
Although the ice VI data are not as good, we can see no evidence of the antiferroelectric ordering
proposed by Kamb from work on recovered samples. Our results are consistent with
thermodynamic measurements indicating disorder in ice VI at 193 K. We conclude that the
orientational ordering behavior of these high pressure ices is simpler than thought previously. For
our ice VI results to be consistent with those of Kamb, his antiferroelectric ordering must be an
artifact of the recovery process, thus throwing doubt on the validity of structural ordering data
obtained on samples recovered to ambient pressure.

recovery, and that these might be responsible for some of the

I. INTRODUCTION
The ice phase diagram is extremely rich, due partly to
the structural versatility inherent in the tetrahedral hydro-
gen-bonding possibilities of the water molecule and partly to
the possibilities of proton ordering. Several phases-espe-
cially the high pressure ones-have been used to explore de-
tails of the water-water interaction.! Recently, the cell vol-
umes, cia ratios, and proton orderings have been used to test
model water-water potential functions that are extensively
used in computer simulation of the pure liquid and more
complex aqueous solutions. Z-4
Many uncertainties remain, however, concerning the
details of the structures of several of these phases. This is
especially so for the highest pressure phases, where implica-
tions concerning proton ordering from dielectric and ther-
modynamic measurements are sometimes in conflict with
the limited crystallographic data available (see Sec. II).
Moreover, much of this crystallographic data were collected
on samples quenched under pressure to liquid nitrogen tem-
peratures, and then recovered to ambient pressure, rather
than on samples within the stability ranges of the respective
phases. Although it appears to be generally assumed that
such recovered samples are structurally similar to the origi-
nal "stable" phases, the possibility remains that structural
changes (especially of the hydrogen ordering) may occur on
apparent discrepancies between crystallographic and other
results.
Thermodynamic and dielectric studies cannot distin-
guish, however, between long and short range order. In con-
trast, the variety of available crystallographic techniques can
make this distinction. These uncertainties and apparent dis-
crepancies can therefore in principle be resolved by neutron
crystallography of both the phases under conditions of sta-
bility and upon recovery. The recent development of high
pressure cells for neutron workS allows powder measure-
ments to be taken throughout the whole of the ice phase
diagram up to pressures of about 3 GPa, and down to liquid
helium temperatures. We present here the results of high
pressure powder measurements on the three (DzO) ice
phases that have interpenetrating sublattices (ices VI, VII,
and VIII). For all three phases, there are uncertainties and
apparent discrepancies concerning the nature and extent of
hydrogen ordering as indicated by published crystallogra-
phic, dielectric, and thermodynamic measurements.
In particular, we present details of the structure of ice
VIII and its proton ordering scheme under conditions of
stability. For ice VII, we have determined the main struc-
tural features, and we are able to put very strict limits on the
possible degree of tetragonal distortion implied by dielectric
and thermodynamic results. Technical difficulties encoun-

3612 J. Chem. Phys. 81 (8), 15 October 1984 0021-9606/84/203612-12$02.10 @ 1984 American Institute of Physics

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 Kuhs et a/. : Structure of ices VI, VII, and VIII
tered with the ice VI experiment means our conclusions on
this phase are less definite. The cell dimensions at three wide-
ly separated temperatures have been determined, and no evi-
dence can be found for any deuteron ordering at any tem-
perature, either in the strong low angle lines or in the
appearance of weaker lines forbidden by the disordered
structure. No structural transition to ice II, IX, or VIII oc-
curs at low temperature, as would be expected from the posi-
tions of the extrapolated phase boundary lines of the current-
ly accepted phase diagram, although in the light of measured
relaxation times6 our ice VI at 8 K could be in a metastable
state.
II. STRUCTURES OF ICES VIII, VII, and VI
A. Ices VII and VIII
There is a general acceptance that both these structures
consist of two interpenetrating, but not interconnecting, cu-
bic (or near-cubic) ice Ic sublattices. 7- 11 Thermodynamic
and dielectric measurements imply that ice VIII is proton
ordered. 8,9,17 There is little direct published crystallographic
evidence for this, or for complete proton disorder in the high
temperature ice VII phase.
Kamb and Davis took x-ray powder data at 223 K and
2.5 GPa. 12 Although this was originally published as the
structure of ice VII, the conditions of measurement are well
within the region of stability of ice VIII, and it must be pre-
sumed that the resulting bec structure (a = 3.30 ± 0.01 A)
deduced from the seven observed lines refers to ice VIII; a
lack of resolution probably prevented the detection of the
tetragonal splitting. Their results were in agreement with
those of Bertie et al. 21 on samples recovered to ambient pres-
sure at presumably liquid nitrogen temperature, and with
the limited single crystal x-ray data of Weir et al., 14 although
the lattice constant clearly varied with the conditions of ob-
servation. A recent high pressure x-ray experiment by Wal-
rafen et al. 15 confirmed the cubic symmetry of ice VII, and
gave the lattice constant at room temperature as a function
of pressure up to 36 GPa.
Apart from the abovementioned low resolution powder
measurements of Kamb and Davis, 12 there are no published
crystallographic data on ice VIII. Most of what is known of
this structure comes from unpublished work of Kamb et al.
quoted in several papers. Johari, Lavergne, and Whalley16
quote x-ray work of Kamb in which the pattern was domi-
nated by a bee structure, with only weak features to suggest a
tetragonal structure. Neutron work of Kamb and Prakash
quoted by Hobbs,8 on (presumably recovered) samples at 108
K suggests a tetragonal distortion of the cubic ice VII struc-
ture, a distortion consistent with the suspected hydrogen or-
dering. Their work on (presumably recovered) samples at
108 K suggests a tetragonal distortion of the cubic ice VII
structure, which the earlier x-ray powder work 12 did not
detect. Such a distortion is consistent with the suspected pro-
ton ordering. The nature of this ordering seems to be as-
sumed to be antiferroelectric, although at least one other
ferroelectric ordering scheme is possible with the same unit
cell. 3 We can find no experimental evidence to clarify which
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3613
ordering scheme is correct. As some models of the water
molecule potential function predict an antiferroelectric or-
dering to be the stable phase, while others favor ferroelectric
scheme, it seems important to clarify this uncertainty.
The thermodynamic and dielectric evidence for hydro-
gen ordering in ice VIII is strong. 9,17 However, similar data
suggests the disorder in ice VII may be incomplete,16.18 and
also that a slight progressive orientational disorder occurs in
ice VIII as the temperature is raised. 16 Quantitatively, the
entropy change across the ices VIII-VII transition is only
80% of that expected for a complete order-disorder transi-
tion. 16 Comparison with the ice III_IX transition suggest a
degree of partial order which is not small (e.g., hydrogen
occupancies shifting from! to about ll. 16 For any long range
order a distortion of the ideal cubic lattice would be expect-
ed,16 which should be detectable in a crystallographic high
resolution experiment. If the disorder is manifest only in
short range correlations of reorienting molecules, the cubic
lattice will not be distorted.
The temperature of the ices VIII-VII transition is ap-
proximately constant over a wide pressure range. For D 20
ice, a transition temperature of - 2.8 ·C was determined by
Pistorius et al., 19 although Johari et al. 16 argue for a correct-
ed value of + 1.1 ·C.
B.lce VI
The oxygen framework of this interpenetrating struc-
ture was determined by Kamb20 from powder and single
crystal data on samples recovered to ambient pressure and
98 K. A space group of P42/nmc was assigned, with cell
dimensions under the conditions of measurement of
a = 6.27, c = 5.79 A. These results were argued consistent
with those of Bertie, Calvert, and Whalley13·21 (again on re-
covered samples), and the limited single crystal measure-
ments under pressure of Weir et al. 14.22 The latter assigned
an orthorhombic space group, but the limitations of the ex-
perimental data led Kamb 20 to argue their results were com-
patible with his data.
Although Kamb 20 noted a weak intensity for the forbid-
den 001 reflection, there is no strong evidence for hydrogen
ordering from his x-ray data. Later, so far unpUblished, neu-
tron data-again on recoverd samples (at 100 K)-quoted in
Kamb 7 claims "strong effects" were observed that were con-
sistent with an antiferroelectric orientational ordering. Al-
though the unit cell dimensions were not changed, a space
group of Pmmn was inferred from the symmetry degrada-
tion indicated by the neutron intensities. Kamb assigns this
partially ordered phase VI'.
Again, there are somewhat different indications from
dielectric measurements made on samples under pressure
under conditions ofstability ofice VI. 18 From these measure-
ments, Johari and Whalley argue the following 6.23 :
(a) Ice VI is partially ordered throughout its stability
range. If it is a long range order, it would be inconsistent with
the assigned space group P42 /nmc. We note that this space
group has not so far been demonstrated to be the correct one
under conditions of stability. However, if the partial order is
 3614 Kuhs et al. : Structure of ices VI, VII, and VIII
a short range correlation of reorienting water molecules, it
would not show up in a decrease of symmetry in our data.
(b) As temperature is reduced, aferroelectric ordering
occurs. This is apparently in contradiction with the above-
mentioned crystallographic indications of an antiferroelec-
tric ordering. As the latter was proposed on the basis of data
collected from recovered samples. a further transition
between 128 K and 9 kbar, and 119 K and ambient pressure
is necessary if both interpretations are to be reconciled.
(c) An unknown, slow, reversible transition occurs at
about 1 GPa and 125 K. lohari and Whalley23 have suggest-
ed a new ice phase is being formed, though no crystallogra-
phic data exist in this region of the phase diagram.
Finally, calorimetric data on the VI-VIII and VI
-VII transitions imply,8 assuming VIII is fully orientation-
ally ordered and VII is disordered, that VI is (within the
limits of the ice rules) fully disordered at this temperature.
However the small slope of the VI~VII boundary16 is not
quite consistent with this conclusion, and it is in conft.ict with
the dielectric indications above, and also with the neutron
data of Kamb, the latter again being for recovered samples.
C.Summary
Thus there are ambiguities and uncertainties concern-
ing these three ice phases which can in principle be clarified
by neutron scattering measurements on samples under con-
ditions of stability. We concentrate in what follows on the
hydrogen ordering in the three phases as indicated by high
resolution neutron measurements on the D 20 ices. Al-
though our results are in some ways only preliminary, we
shall conclude that the ordering situation seems simpler than
thought to be in the (admittedly rather confused) literature.
Apparent lack of changes in relative intensities as the tem-
perature of ice VI changes do not lend support for Whalley'S
postulated gradual deuteron ordering to be oflong range,6.23
and suggest that ice VI at all temperatures is disordred, in
agreement with thermodynamic data. 8 This result raises
queries concerning structural data obtained from samples
recovered to ambient pressure. Although times allowed for
relaxation at lower temperatures are probably too restricted
to allow a definitive statement on the matter, we see no struc-
tural indications of the start of a transformation to the new
phase suggested by Whalley et al. 23 There exist however fer-
roelectric ordering schemes within a bigger tetragonal unit
cell which would cause only little intensity changes on order-
ing. If there should be any (partial) ordering, we would ex-
pect this to take place in a ferroelectric manner.
III. EXPERIMENTAL
A. Sample preparation and loading
As automatic sample rotation was not possible within
the cryostat, it was essential to prepare a. fine powder. Con-
sidering the ice phase diagram, the pressure cell had to be
loaded at low temperature (:S - 20°C) to prevent the possi-
bility of melting occurring. Accordingly, high purity
(99.85%) D 20 was placed in a mortar in a glove bag, liquid
nitrogen added, and the resulting ice powdered finely with a
pestle. This was then transferred with a cooled spatula to a
liquid nitrogen cooled aluminium can (dimensions 13 mm
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height X 4 mm diameter) and pressed down in the can tightly
to obtain as large a sample as possible. This procedure was
repeated until the can was full, after which it was closed with
a close-fitting aluminium cap.
Meanwhile the pressure cell of the clamped typeS was
cooled in liquid nitrogen, from which it was removed brieft.y
to allow the placing of the sample in alumina cell within the
vessel. A pressure of 0.5-0.6 GPa was applied immediately
by bolting down the top of the cell after which it was reim-
mersed in liquid nitrogen and transferred to a hydraulic
press for loading. Loading was performed slowly, car being
taken to reload after any slow relaxation had taken place. A
dramatic explosive drop in pressure occurred during load-
ing, presumably related to the large volume change expected
on the formation of ice VI, the first high density phase that
would be encountered during loading. The nominal loaded
pressure was checked at the completion of the diffraction
experiments.
Two separate experiments, one for ices VII and VIII,
the second for ice VI, were performed with two different
samples on two different occasions.
The pressure cell was loaded in a standard cryostat suit-
able for use with the cell.
B. Data collection
Data was collected on the DIA high resolution powder
diffractometer at the Institut Laue-Langevin, Grenoble. 24
Wavelengths were calibrated using an alumina powder, and
the degree of preferred orientation of the samples monitored
by measuring several of the strongest peaks as a function of
the omega angle. Dummy measurements of a separate alu-
mina cell were made (outside the pressure cell and cryostat at
room temperature) at all wavelengths used to assist in the
identification of sample peaks from the rather complex alu-
mina pattern.
The temperature was controlled by He gas ft.ow and
monitored by a Si diode mounted directly on the pressure
cell approximately 11 cm from the sample. Due to the rela-
tively large mass of the pressure cell (-4.5 kg) thermal equi-
librium was reached slowly, typically within 3 or 4 h. The
final temperature gradient between the sample and the sen-
sor position was measured with a dummy device to be
smaller than 2 K.
For ice VIII, data were taken at 2.4 ± 0.1 GPa and
10 ± 1 K at 1.390(2) A, and continuous scans taken as the
temperature was raised slowly (0.5 kmin-I) up to the VIII
-VII transition. The temperature was stabilized at the tran-
sition for several hours, and several scans made at 2.988(2)
A. The ice VII data was taken without cryostat at 2.4 ± 0.1
GPa and 295 ± 2 K, again at 1.390(2) A. Data sets for both
phases were also collected at 2.988(2) A. The high wave-
length data were used to establish the unit cell parameters
accurately, and, in the case of ice VII, to check for any split-
ting of the 110 (cubic) which would indicate a tetragonal
structure resulting from orientational ordering.
The 1.909 A scans facilitated better separation of the
112 and 200 (tetragonal) ice VIII peaks for intensity extrac-
tion. Figure 1 shows the scans of the ice VII and VIII sam-
ples at 295 and 10 K, respectively, for a wavelength of
1.390(2) A.
 Kuhs 6t at : Structure of ices VI, VII, and VIII 3615

~
Z
=:J
o
U

500

250

o FIG. 1. (a) Neutron dift'raction

o 25 50 ,5 100 125 150
pattern for ice VIII at 10 K and
2THETA IN DEGREES
2.4 GPa. The sample peaks are
shown in black and their Miller
indices hkl are given. Note the
considerable scattering from
the Al20 3 pressure cell. (b)Sim-
ilarly the neutron diffraction
~
pattern for ice VII at 295 K and
Z 2.4 GPa.
=:J
o
U

150

500

250

o
o 25 50 75 100 125 150
2THETA IN DEGREES

In the ice VI experiment, data were collected at the

same three wavelengths, initially at 1.1 ± 0.1 GPa and
225 ± 2 K. This temperature is well within the stability
range of this phase, and one at which deuteron ordering is
expected to be relatively small, if any exists at all. To look for
possible hydrogen ordering, the temperature was lowered to
125 ± 1 K and scans taken at 2.988(2) A. The average cool-
ing rate of 0.4 kmin - J was sufficiently slow to prevent
quenching, according to the dielectric relaxation time mea-
surements of Whalley et al. 6 A final 2.988 A data set was
taken at 8 ± 1 K after cooling at an average rate of 0.5
kmin-t.
IV. DATA TREATMENT
In all cases, the 2.988 Adata were used to determine the
lattice parameters and the 2 () offset by least squares fitting.
Integrated intensities were obtained by least squares fitting
of Gaussian (or Lorentzian) curves to the measured profile.
The procedure allows for up to five overlapping peaks, and
gives also the error of the fit parameters (position, height,
width, slope, and height of background). For overlapping
peaks (including overlap with background alumina lines),
the peak positions (known from the previous lattice param-
eter and offset refinement) and the widths (obtained from

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 3616 Kuhs et al. : Structure of ices VI, VII, and VIII

calibration curves derived from single peaks) were fixed. The

intensities so obtained were then corrected for Lorentz ef-
pdj(u) = pdj(u)Oaussian .[1 + -br.H
3!
3(u)
fects and where necessary for multiplicity.
An independent set of intensities for the nonoverlap- (2)
ping peaks of the ice VII and VIII data were obtained by
numerical integration using Simpson's rule. These agreed whereH3 (u), H4(U) are Hermite polynomials of order 3 and 4,
within 1-2 standard errors with the more sophisticated pro- respectively.
file fitting, and are not discussed further. The second approach is especially well suited for orien-
Crystallographic least squares refinements were per- tationally disordered structures. One starts with a complete-
formed using the extracted intensities. Initial refinements ly disordered situation (i.e., homogeneous distributions on
were done using the PROMETHUS system 25 at the ILL and spherical surfaces) and introduces modulations of this distri-
the SHELXTL system26 at the SERC Daresbury Laborato- bution by inclusion of symmetry adapted surface harmon-
ry. Within estimated errors, the two sets of results were con- ics. 28 The corresponding structure factor expression is given
sistent, and only the more extensive calculations using PRO- as
METHEUS are discussed further. The highly disordered F(Q) = "iJj.exp(iroQ)·exp[ - Wj(Q)].F?t(Q) (3)
j
structure of ice VII was difficult to describe within the limit
of the harmonic approximation for thermal motions. Higher with the rotational structure factor F?t(Q) given as
order thermal parameters were refined in an attempt to mod- F?t(Q) = 41TiJ/(Q,p)Clm kim (I1Q)' (4)
el the atomic probability density distributions. Two different
wherejIlQp) are the spherical Bessel functions with argu-
approaches were found to be useful in this case.
ment Qp' p is the radius of the shell (i.e., the distance from
In the first the harmonic structure factor expression is
the center of mass), Clm are expansion coefficients of the
expanded to include higher order thermal tensors in a so-
symmetry adapted surface harmonics Kim and 11 Q denotes
called quasimomentum expansion. 27
the polar angle of the scattering vector Q. The expansion
coefficients Clm are adjusted in a least squares refinement.
F(Q) = "iJj exp(ixjQ).exp[ - Wj(Q)] The corresponding probability density function is readily
j
calculated according to
(1)
pdj(r) =I IClm(r).Klm(l1r)' (5)
Wj(Q) is the harmonic temperature factor, Q the scattering I m

vector,jj the neutron scattering length of atomj, and rj' 8j
are the anharmonic thermal tensors of order 3 and 4, respec-
tively. The components of these tensors are adjustable in a
least-squares program like PROMETHEUS. 25 Using these
refined parameters the atomic probability density distribu-
tion might be calculated according to
I1r denotes the polar angle of positional vector r. In its sim-
plest form this approach does not contain any coupling
between rotations and translations of the molecule. Trying
to refine more sophisticated models including correlations
between orientation and position of the molecule 29 would
certainly mean overestimating the quality of the available

TABLE I. Lattice parameters and densities of ices VIII, VII, and VI. a

p(mgmm- 3 )b

T(K) alA) cia 0 20 H2O

Ice VIII 10(1) 4.656(1) 6.775(1) 1.4551(5) 1.810 1.628

Liq. N/ 4.80 6.99 1.456 1.66 1.49
263(2) 4.669(3) 6.810(4) 1.4586(20) 1.791 1.611
Ice VII 263(2) 3.337(2) 1.789 1.609
295(2) 3.344(2) 1.778 1.599
Liq. N 2d 3.41 1.68 1.51
Ice VI 8(1) 6.166(1) 5.689(1) 0.9226 1.535 1.381
98< 6.27 5.79 0.923 1.46 1.31
125(2) 6.170(1) 6.691(1) 0.9224 1.533 1.379
225(2) 6.1812(5) 5.6980(4) 0.9218 1.526 1.373

a Lattice parameters are obtained by least squares fitting of selected, well resolved reflections. Errors are given
in brackets.
bThe densities calculated from our 0 20 data and the densities given or calculated from the literature are
renorma1ized for H 20 and 0 20, respectively, under the assumption of identical lattice constants for H 20 and
0 20 ices.
C From unpUblished work by Kamb and Prakash cited in Ref. 8.

dQuenched (pseudocubic) ice VII at ambient pressure (Ref. 12).

< Quenched samples (Ref. 20).

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 Kuhs sf al. : Structure of ices VI, VII, and VIII 3617

TABLE II. Positional and thermal parameters ofice VIII at 10 K and 2.4 GPa (space group I 4[ lamd; origin at
center)."

Coordinates (Equiv.) Anisotropic

Fractional isotropic temperature factor"
Atom x y z B (A2)

o 0.0 0.25 0.1071(12) 0.58(17) not refined

D 0.0 0.4157(15) 0.1935(8) 1.54(14)C U 11 = 0.0240(46)
U 22 = 0.0181(39)
U 33 = 0.0164(31)
U 23 = _ 0.0024(26)

• The refinement was done on the observed structure factors Fo. The final crystallographic R factor (Fe denotes
thecalculatedstructurefactor)R = ~ \Fo - Fe I!~Fo was 0.068. The final weightedR factorforrefinementon
Fo, Rw = [~w(Fo - Fcf/~wF~]'/2 with weights w = l/o{F)2 was 0.053. The goodness-of-fit
S = [~w(Fo - Fe )2/INo - Np )] 1/2 with No = number of observations and Np = number of parameters was
0.71.
bThe temperature factor expression used is exp[ - 2r(h 2a 2U" + k 2b 2U 22 + /2Clu 33 + 2hka*b *U '2
+ 2k (b *c* U 23 + 2lhc*a* U 13].
C Calculated from the refined CJII coefficients.

data; data sets with higher accuracy and extending to higher is consistent with Walrafen et al. 1s recent x-ray results.
Q values than those measured are clearly needed. These smaller lattice parameters under conditions of stabil-
A Rietveld profile refinement on the ice VIII data was ity imply higher densities and shorter hydrogen bonds; these
also performed using the Cambridge Crystal Structure Li- points are discussed further below. The volume change at the
brary procedures as implemented on the NAS7000 at the transition is effectively zero.
SERC Daresbury Laboratory. 30 Again, the results were con-
sistent with the simpler least squares refinements, and as no B. Ice VIII refinement at 10K
significant advantage was offered by profile refinement in Intensities for 43 reflections were extracted, and stan-
this investigation, it was not pursued further. dard least-squares refinement performed using 32 of these.
Most of the 11 reflections not used were rejected because of
V. RESULTS: ICES VII AND VIII relatively large uncertainty consequent on the difficulty of
A. Lattice constants and symmetry extraction from overlapping alumina lines. Refinement was
That ice VIII is clearly tetragonal is shown by the separ- performed of nine parameters in the nominal tetraBonal
ation of the 112 and 200 peaks, indexed with respect to the
expected unit cell, at the 2.988 A wavelength. On passing
through the VIII/VII transition, these two peaks merge to
yield one 110 reflection (indexed with respect to the expected
ice VII unit cell), whose width was no larger than expected
for a simple peak. A detailed analysis of this peak shape and
width showed absolutely no evidence of its being due to two
very close, overlapping peaks. Considering the very high re-
solution ofDIA and the high wavelength used, we conclude
that ice VII is indeed cubic, any deviation from cubicity must
be smaller than 0.09% in terms of the cubic lattice constant.
From the unit cell symmetry, we have no evidence that VII is
partly orientationally ordered in a manner similar to VIII.
Similarly, considering the constancy of the relative intensi-
ties of the ice VIII peaks as the transition temperature is
approached, there is no evidence here for any significant
deuteron disordering as ice VIII approaches the transition
temperature. The possibilities of partial disordering in VIII
and partial ordering in VII are discussed further below.
Table I gives the refined lattice parameters, together
with the implied densities and comparisons with the litera-
ture values which refer to recovered samples at low tempera-
tures and at ambient pressure. As might be expected, the
lattice parameters under pressure are significantly smaller
FIG. 2. The structure of ice VIII at 10 K and 2.4 GPa. The thermal ellip-
than in the ambient pressure recovered samples; the c/a ra-
soids are scaled to enclose 50% probability. Note the anisotropy of the deu-
tios of the tetragonal ice VIII are almost identical in the high teron thermal motion. White and black bonds mark the molecules belong-
pressure and recovered samples. The ice VII lattice constant ing to the two independent sublattices. Thin lines mark the hydrogen bonds.

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 3618 Kuhs et al. : Structure of ices VI, VII, and VIII

TABLE III. Bond distances (A) and angles (0) in ice VIII at 10 K and 2.4
GPa.

Atoms Distance or angle

0-0 bonded 2.879(1)
0-0 non bonded 2.743(9)
O-D 0.9685(71)
O-O-D 105.61(1.06)
0-0-0 bonded average 109.474
O···O-O-D···O 107.92(3)
0 .. ·0-0 .. ·0-0 11O.25( 1) multiplicity 4
O-D .. ·O .. ·o-o 107.92(3)
O-D .. ·O 178.25(70)

space group I4)/amd. The thermal motions of the oxygens

were constrained to be isotropic, with free refinement of the
harmonic deuteron thermal parameters. A final crystallo-
graphic R factor of 0.068 was obtained rapidly. 3) The result-
ing structure parameters (Table II) are consistent with an
antiferroelectrically ordered structure shown in Fig. 2.
To examine the possibility of partial deuteron disorder-
ing, a further refinement of the deuteron population was per-
formed in the same space group. In this refinement, the
bonded O-D distance and the thermal parameters were ef-
fectively constrained. The result was unambiguous, yielding
a deuteron site population of 1.008(17). We thus conclude
that the deuterons are fully ordered in ice VIII at 10 K and
2.4 GPa. Inspection of relative intensities as the temperature
was raised up to the transition temperature showed no evi-
dence for partial disordering, although the shorter scans
used mean a greater uncertainty in this conclusion.
The possibility of a symmetry reduction in a tetragonal
cell was also examined by checking the refinement in three
lower space groups in each of which one symmetry element
is removed. In each of/4m2 and I 4)md, there are two differ-
ent fully ordered deuteron positions. The symmetry reduc-
tion on I42d as well as in I4)22 or I4)/a corresponds to a
molecular tilt, which displaces the deuterons out of plane. In
all cases, no significant improvement in the refinement was
obtained. Thus there is no indication of a symmetry reduc-
tion, and we therefore conclude that the adopted space
group I 4)/amd is probably correct.
The stereochemistry of the water molecule in ice VIII
(Table III) is unremarkable, and gives us confidence in the
quality of the data. The order of magnitude of the deuteron
temperature factors (Table IV) is about what would be ex-
pected from other ice phases; there is little reason to expect
TABLE IV. Ellipsoids of vibration in ice VIII at 10 K and 2.4 GPa.
Orientation of ellipsoidal
Root mean square Angle (") with
Atom displacement (A) a axis baxis
0 0.0854(78) isotrop
D 0.1213(121) 90 54.60
0.1405(135) 90 144.60
0.1550( 149) 0 90
FIG. 3. Probability density of the oxygen atom in ice VII at 295 K and 2.4
GPa. The plane shown is perpendicular to one of the cubic main axes. The
excess of density along the two remaining main axes is clearly visible. Note
the resolution limit indicated in the frame.
large differences in the zero point motion that is dominant at
this temperature. The anisotropy of the thermal motions is
sensible, and is depicted in Fig. 2. Within (quite large) error
limits, the shortest axis of the thermal ellipsoid is parallel to
the O-D bond, while the longest axis is normal to both the
O-D bond and the DOD plane. The intermolecular geome-
try at this high density is of particular interest, as there were
indications from the work on recovered samples that the
non bonded 0· ..0 distance might be shorter than the hydro-
gen-bonded contact. This is confirmed by our ice VIII re-
sults, which give a shortest nonbonded 0···0 distance of
2.743(9) A, significantly shorter than the hydrogen bonded
distance of2.879( I) A. The noncubic symmetry forces a defi-
nite deviation from perfect tetrahedrality in the hydrogen-
bonded 0 ..·0..·0 angle.
C. Ice VII refinement at 295 K
The initial refinements in which was assumed an orien-
tationally disordered arrangement of the deuterons on one
set of 8(g) sites in the space group Pn3m, converged rapidly
to a crystallographic R factor of 0.049 for 15 intensities that
could be reliably extracted.
To investigate the possibility of partial deuteron order-
ing, in addition to the test for peak splitting discussed above,
refinements in lower symmetry space groups that permitted
ordering were considered. As only a relatively small number
of intensities were available, this exercise was limited to
searching the scans for evidence of weak superlattice peaks
that might indicate a different space group. None were
found, implying any partial ordering at room temperature is
probably weak. The lower temperature scans close to the
transition were also examined for superlattice peaks again
with no positive result. Similar to the high temperature ice
caxis VIII data in comparison to that at 10 K, the statistics of the
lower temperature ice VII data were poorer than at room
temperature; within these limitations, however, we see no
35.40
54.60
crystallographic evidence for partial ordering in ice VII.
90 The results of the initial refinements clearly gave O-D
distances, which were much smaller than expected (:::::0.89

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 Kuhs et al. : Structure of ices VI, VII, and VIII
[111]
[001]
FIG. 4. Model of the orientational disorder in ice VII. Out of 6 possible
orientations of the molecule only one is shown. The oxygen atom positions
are given as black spheres located on the main axes and the deuteron posi-
tions as black ellipsoids located on one set of body diagonals. The tetrahe-
dral angle r is decreased to give the water angle", by introducing the oxygen
disorder. All oxygen positions are located on a sphere with its center at the
intersection of the main axes and the body diagonals through the deuterons.
A); the possibility that this might be solely an artifact caused
by strong librations of the deuterons was examined, and led
to a distance, which was longer (:::;:0.91 A), but still too small.
Therefore to retain the normal O-D distances (:::;:0.98 A) the
oxygen atoms must be disordered. Different split models
were tested; none of these could be freely refined, since the
available data set is too limited in Q to allow for resolving the
complex oxygen probability density. At this stage anhar-
monic nonsplit models using Eq. (2) (with the oxygen atoms
fixed at the position 2a of space group Pn3m) were employed
in order to reduce the correlation problems encountered in
TABLE V. Structural parameters of 10 VII at 295 K and 2.4 GPaa. b (space
group Pn3m).
rox 0.0963(55) A
U;.o 0.0250(6) A2
e31 1.563(16)
e41 - 1.308(54)
e61 1.392(49)
e71 - 0.957(91)
e81 1.629( 197)
• Refinements were performed with the model shown in Fig. 3 using Eqs. (3)
e,m
and (4); are the expansion coefficients of the symmetry adapted surface
harmonics.
b The final crystallographic R factor was 0.033 obtained in a refinement on
the observed intensities. The weighted R factor was 0.014 and the good-
ness-of-fit 0.44 (for a definition of these quantities see Table II). The mode
positions (maxima of the probability density) are located on the [111] axes.
The fractional coordinates of the mode are x, x, x with x::::: 0.410; the frac-
tional coordinates obtained from a conventional refinement are x, x, x
with x::::: 0.408 after correction for librational thermal motions.
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3619
refining conventional split models. 3 ! This approach gave
converging refinements; with one additional parameter
(15 1122 = - 0.038(18)X 10- 4 ) the crystallographic R factor
dropped to 0.037. The resulting oxygen probability density
calculated with Eq. (2) is shown in Fig. 3.
Due to the Q limitations of the data set the oxygen dis-
order was not resolved (note the resolution limit given in Fig.
3), but clearly there is either a strongly directional thermal
motion or a real disorder along the [loo] directions. These
findings led us to try a structure model, which is more re-
strictive to the water molecule geometry in order to get more
information on the oxygen displacements. This model is
sketched in Fig. 4. The deuteron distribution is described by
symmetry adapted surface harmonics [see Eqs. (3) and (4)],
while the oxygen atoms are assumed to be equally distribut-
ed on a sphere around the high symmetry 4a site of space
group Pn3m. No attempt was made to model further the
oxygen density, since the limited data set is not sensitive to
small modulations in real space. The geometry of the water
molecule was fixed with O-D distances equal to 0.985 Aand
D-O-D angles equal to 104.5". On the other hand the radius
of the oxygen shell was freely refined. The refinements con-
verged to a final crystallographic R factor of 0.033 with pa-
rameters given in Table V. 3 ! Releasing the constraint on the
O-D distance gave a slightly larger value [1.016(17) A] with-
out any essential changes in other parameters. As expected
from the conventional refinements the deuteron atoms are
located at one set of [Ill] axes forming in the average tetra-
hedral surrounding around the midpoint of the oxygen shell.
A stereographic projection of the probability distribution on
the deuteron shell is shown in Fig. 5. Whether the slight, but
significant assymmetry of the deuteron density (higher den-
111
o
100 110
111
FIG. 5. Stereographic projection of the deuteron probability density in ice
VII at 295 K and 2.4 GPa. The density maximum clearly is on one set of the
body diagonals. The smaIl density maximum on the main axes is probably
not significant.
 3620 Kuhs et al. : Structure of ices VI, VII, and VIII
sity towards [llO], lower density towards [100]) is indicating
an additional disorder with bent hydrogen bonds or simply
some preferred librational motion, cannot be decided on
with the present data. The refined radius of the oxygen shell
[0.0963(55) A] is only slightly shorter than the distance
between an oxygen atom and the center of gravity of a 0 20
molecule (0.12 A). Combining these findings with results ob-
tained from anharmonic nonsplit models suggest that in ice
VII at 2.4 GPa the 0 2 0 molecules are orientationally disor-
dered approximately around their center of mass; there are
six principally different molecule orientations involving (at
least) four possible hydrogen sites located on (or close to) one
set of body diagonals and six possible oxygen sites located on
the main axes.
D. The VII-VIII phase transition
Scans at 2.988(2) A were taken at the phase transition,
after allowing several hours for the temperature to stabilize.
Coexistence of the two phases was observed, of about a 501
50 composition. This coexistence implies either a tempera-
ture gradient across the sample, or some hysteresis. Subse-
quent small temperature changes of about 1 K in both direc-
tions imply that any such hysteresis must be relatively small,
and the transition itself sharp. The temperature of the transi-
tion was fixed at 263 K.
The measured temperature gradient between the sam-
ple and the thermal sensor implies an uncertainty in the tran-
sition temperature of less than 2 K. Thus our data suggests
the 0 20 VII-VIII transition temperature is some 11 K low-
er than reported by Johari et al. 16 from dielectric data, and 8
K lower than the results of Pistorius et al. 19
As shown in Table I, within the limits of the errors, the
0 .. ·0 distance in VII [2.890(1) A] is indistinguishable from
the hydrogen-bonded 0···0 distance in VIII [2.889(1) A] at
the transition. The densities are also the same.
VI. RESULTS: ICE VI
A. Lattice constants
From the high wavelength data, after fixing the posi-
tions of the strongest peaks that were least affected by alu-
mina lines as described above, the lattice parameters at the
three temperatures were determined as in Table I. As with
ices VII and VIII, the lattice constants under pressure are
significantly lower than for the recovered samples by about
1.5% while the cia ratio again is very similar. The resultant
calculated density (corrected to H 20) is some 5% higher
than for the 98 K and ambient pressure recovered material. 20
B. Possible orlentatlonal roderlng
Because of severe problems of overlap with Al20 3 peaks
from the pressure cell, the quality of the data obtained on ice
VI was significantly poorer than for either VII or VIII. In
the initial stages of the data analysis, it was felt that, bearing
in mind the large number of independent parameters that
needed to be refined, an unrestrained refinement was not
justified. Instead, using the postulated space group P 421
nmc, expected intensities were calculated, assuming initially
no hydrogen ordering. For this calculation, deuterons were
placed in the oxygen framework to give water molecules
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with sensible geometry. The intensities so calculated agreed
within the estimated errors with those measured experimen-
tally at 225 K.
The calculated intensities were extremely sensitive to
small shifts in deuteron positions, and only for good molecu-
lar geometry was agreement with experiment obtained. Ac-
cordingly, we were encouraged to perform intensity calcula-
tions for a variety of deuteron partial orderings. These initial
calculations were performed within the same space group
(which permits only orderings which violate the ice rule;
apart from very small degrees of partial order, the strongest
intensities were so altered as to be outside even the relatively
large errors in our intensity measurements.
C. Ordering in other space groups
The different ordering schemes suggested by Kamb 7
(recovered samples, antiferroelectric proposed ordering) and
Johari et al. 6 (under pressure,ferroelectric proposed order-
ing) involve space groups other than the P 421nmc assigned to
the fully disordered phase. Thus, in order to test possible
ordering schemes of either type, it is necessary to check out
data against structures in those possible space groups that
are consistent with hydrogen ordering. Accordingly, we
have checked all possible tetragonal, and some ofthe ortho-
rhombic space groups, down to the third level.
A ferroelectric full ordering in a tetragonal lattice is
permitted in P4, P42c, P42b, 142c, 14, P42 1c, P42 , P42 bc,
and 14 1cd. In contrast, antiferroelectric ordering is possible
in only one tetragonal space group, namely 141/a. All these
space groups demand a larger unit cell compared to that
presently adopted in P42lnmc. Thus, we do not agree with
Johari et al. 6 who propose that full ferroelectric ordering is
possible in P 42 mc. Our examination of this space group sug-
gests it is not consistent with a full range of deuteron disor-
dering for the deuteron 03 (see Table VI) which is related by
the mirror plane. The full range of ordering is possible for the
other deuterons.
At this stage, our discussion of possible ordering can
only be preliminary, because of the problems with the data,
in particular overlap with alumina peaks. A detailed check
for broadening of specific peaks as temperature is lowered
shows no measureable effect; we conclude that any ortho-
TABLE VI. Positional and thennal parameters of ice VI at 225 K and 1.1
GPa (spacegroup P4 2 /nmc, origin at center).'
Fractional coordinates
Atom x y z Isotropic Bb
01 0.15 0.25 0.15
0.1339(38) 2.99(49)
02 0.15 0.5295(43)
Dl 0.15 0.4628(92) - 0.0131(86)
D2 0.15 0.3103(64) -0.1365(101)
D3 0.15 0.6812(10) 0.1248(18) 3.80(51)
D4 0.1325(41) 0.5301(51) 0.1844(51)
'The refinement was done on the observed structure factors. The final crys-
tallographic R factor was 0.103; the fina1 weighted R factor was 0.039 and
the goodness-of-fit 0.68 (for a definition of these quantities see Table II).
bThe thennal parameters were constraint to be identical for all oxygen
atoms and for all deuterium atoms.
 Kuhs et 81. : Structure of ices VI, VII, and VIII 3621

rhombic splitting must be very small, and ofthe same order
as in the ice VII case. Moreover, a careful check revealed no
sign of expected superlattice peaks, either for the tetragonal
space group (I41/a) or lower orthorhombic space groups.
Although all possibilities could not be definitely checked be-
cause of alumina overlap, the balance of evidence with re-
spect to the absence of both superlattice peaks and lattice
distortion leads us to suggest that ice VI at low temperature
is not antiferroelectrically ordered. Although we cannot en-
tirely rule out the ferroelectric ordering possibility, we have
no positive experimental evidence to support it. Moreover,
for partial orderings, a whole series of further space groups
have to be considered (some of them with a cell identical to
that presently adopted in P42/nmc). These should show at
least a few extra peaks which, because of the order being only
partial, could be weak. We see no evidence of such weak
peaks, but cannot at present rule them out categorically.
As a further examination of possible ordering as the
temperature is lowered, a detailed comparison of the relative
intensity changes of the strongest, background-unaffected
peaks was performed. In extracting these intensities from the
2.988 A data, 2(} values were fixed from the lattice param-
eters, and most peak widths fixed from a previously plotted
resolution curve. Within the errors estimated, there were no
detectable relative intensity changes between any of the
three temperatures. Although our data is not totally ade-
quate to make a definitive statement, we conclude on the
balance of the evidence that as the temperature falls any
significant antiferroelectric ordering is very unlikely and fer-
roelectric ordering is at least not supported by the direct
crystallographic data. Further work is under way to reduce
the uncertainty in the present discussion by taking data with
an improved pressure cell.
D. The structure of Ice VI
A detailed inspection of the data finally allowed 32
peaks to be extracted reasonably confidently from the alu-
mina lines. The 211 gave particular problems, being over-
lapped by two overlapping alumina peaks. As the ice peak
was best separated out from the alumina pattern in the 8 K
data (due to the relative shift of the cell parameters), the 211
intensity was assigned on this basis, and a structure refine-
ment in P 42 /nmc of the positional parameters for the 225 K
data set performed. The deuterons were assumed fully disor-
dered. Two isotropic temperature factors were refined, one
each for all the oxygens and all the deuterons; the final crys-
tallographic R factor was 0.103 31 with parameters given in
Table VI.
Although we do not regard these results as definitive,
they are sensible in terms of molecular geometry, and we
therefore present the main structural data in Table VII. The
bonded 00 distances are generally shorter than for ice
Ih(l.OI A), not unexpected considering the lower symmetry
in ice VI, and hence smaller resonance effects. Even consid-
ering the large errors, there is evidence of dispersion in the
00 distances, and also in the DOD angle, which is clearly
different from the vapor value of 104.5°. The average is very
close to tetrahedral (109.47°). Hydrogen bond distances are
shorter than those in VII and VIII, and the hydrogen bond
angles themselves are significantly nonlinear. The 0···0···0

TABLE VII. Bond distances (A) and angles (") in ice VI at 225 K and 1.1 GPa.

0-0 bonds
0-0 distances or D-O-O and
Central or andO-D-O
atom Atoms 0-0-0 angles Atoms angles Multiplicity

01 01-02 2.788(24) 01-02 0.986(48) 4

02 02-01 2.788(24) 02-01 0.937(55) I
02-02 2.726(38) 02-03 0.976(51) I
02-02' 2.778(28) 02-04 0.939(32) 2
Average" 0-0 2.774 0-0 0.961
01 02-01-02 128.02(45) 02-01-02 115.51(2.29) 4
76.60(73) 97.97(4.77) 2
02 01-02-02' 89.32(78) 01-02-04 105.67(3.40) 2
01-02-02 128.30(96) 01-02-03 113.07(4.86) I
02'-02-02' 76.90(92) 04-02-04 101.29(3.40) I
02-02-02' 128.45(75) 03-02-04 114.97(2.92) 2
Average" 0-0-0 108.15 0-0-0 109.40
01 01-01-02 161.81(5.19)
02 01-02-02 163.58(4.41)
03 02-03-02 175.22(4.33) I
04 02-04-02 156.64(3.09) I
01 01-02 nonbonded 3.442(11) 8
02 02-01 nonbonded 3.442(11) 2
02-02 nonbonded 3.466(14) 2
02-02' nonbonded 3.340(29) 4
02-02" nonbonded 3.456(38) I
Average" 0-0 nonbonded 3.411

• The average is calculated taking into account the absolute frequency of occurrence.

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 3622 Kuhs et al. : Structure of ices VI, VII, and VIII
angles cover a wide range from about 76° to 128°, as found in
the recovered samples. Compared to ices VII and VIII the
nonbonded 0-0 distances are considerably larger with an
average value of 3.41 A.
VII. CONCLUSIONS
Using powder refinement, we have studied the struc-
tural details of ices VI, VII, and VIII under their expected
conditions ofstability. Although the ice VI data are of signifi-
cantly poorer quality than those for the other two phases, we
have established accurate cell dimensions for all three
phases, and the intensity data are consistent with space
groups P42 /nmc, Pn3m, and P4 1/amd, respectively. In all
cases the 0 20 molecule geometry was found to be quite nor-
mal.
We have established clearly the basic structural fea-
tures of ices VII and VIII. The low temperature phase ap-
pears fully ordered, and we have no structural evidence for
partial hydrogen ordering of ice VII. Any partial ordering,
such as that implied by the dielectric data of Johari et 01.,18
must be restricted to short range correlations of reorienting
water molecules.
The oxygen atoms in ice VII were found to be disor-
dered probably along the [100] directions of the cubic lattice.
The hydrogen atoms are disordered among positions located
at one set of [111] axes with a constant distance from a point,
which is close to the center of mass of a water molecule.
Clearly such a time and space averaged picture of atomic
density distributions cannot conclusively define the true na-
ture of disorder; nevertheless these findings suggest a possi-
ble rotational disorder of the 0 2 0 molecules around their
center of mass. One might expect that such a hindered rota-
tion freezes in at a certain temperature, thus transforming
easily into an ordered structure. With increasing pressure
the large 0···0 distances become considerably smaller,
therefore the steric hindrance increases, while the hydr~gen
bonding gets stronger. This means ice VII is losing more and
more its molecular character, leading eventually to a sym-
metric hydrogen bond as suggested by Walrafen et 01.15
The transition between the two phases is sharp and re-
versible, and occurs at 263 ± 2 K. This is some 11 K lower
than previously thought for 0 20; even considering the possi-
bility of temperature gradient across the sample, we cannot
argue for a significantly higher transition temperature.
Further data on both phases just above and just below the
transition temperature will be required to establish higher
limits on possible disordering of VIII at high temperature,
and ordering of VII at low temperature. Our continuous
scans in this region do not allow anything more than a rela-
tively small amount of disorder or order in each respective
case.
We have confirmed that the nonbonded first neighbor
distance is significantly shorter than the hydrogen bonded
first neighbor distance in ice VIII. The hydrogen bond ap-
pears to be the same length in the two phases at the transi-
tion, and the densities equal.
Our conclusions on ice VI are less clear, due to severe
overlap problems with the alumina pattern from the pres-
sure cell. The lattice constants at 8, 125, and 225 K have been
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established under pressure for the first time. Both the molec-
ular and hydrogen bonding geometry are less perfect and
more dispersed for VI than for VII and VIII. The intramole-
cular HOH angle for VIII is consistent with the vapor phase
value, while in VI there are significant distortions to both
larger and smaller angles. Oespite this significant scatter, the
average is interestingly almost tetrahedral. As we do not see
how this could be forced by symmetry, we might hypoth-
esize that this again implies at least a partially disordered
hydrogen arrangement. Hydrogen bond distances are much
shorter in VI than in VIII, presumably being forced longer in
the latter case by the greater packing density of the oxygens.
The nonbonded 0-0 distances are considerably larger in ice
VI than in VII, the interaction between the independent sub-
lattices therefore being certainly different in ice VI and VII.
Hydrogen bond angles in VII are almost linear, but signifi-
cantly bent and dispersed in VI, as are the 0···0···0 angles.
Concerning partial ordering of the deuterons, our di-
rect structural results do not support the earlier crystallogra-
phic work of Kamb, 7 who postulated an antiferroelectric
ordering in recovered samples. There is no evidence at any of
the three temperatures for peak splittings or superlattice
peaks which would signal an antiferroelectric ordering, nor
can we detect either significant intensity changes or the ap-
pearance ofsuperlattice peaks which would denote a ferroe-
lectric (partial) ordering. Further work is proposed to con-
firm these conclusions, and to put tighter error bars on
possible ferroelectric (partial) orderings, but the balance of
our evidence suggests these ordering processes are not oc-
curring to a significant degree. This conclusion is based on
the assumption that any ferroelectric ordering will result in
at least small rearrangements of the interatomic distances
and angles, which would show up in the scattered intensi-
ties?3 Ifwe are correct, we will be consistent with thermody-
namic evidence that ice VI is disordered at 193 K and any
partial order such as that implied by Johari and Whalley6.23
dielectric data must be due to short range correlations as in
ice VII. Our results are consistent with those of Kamb 7 on
recovered samples only if the antiferroelectric transition re-
ported by Kamb occurs as a result of the recovery process. If
the necessary further work shows this to be the case then the
validity of using structural ordering data from recovered
samples is in doubt.
No changes were observed in cooling ice VI to 8 K. At
our cooling rates, we would not expect to see any sign of the
slow transition postulated by Johari and Whalley.23 That no
transition to a different ice phase was observed implies either
that our sample was effectively quenched, or that the stabil-
ity range of ice VI extends to lower temperatures than would
be implied by extrapolating the phase boundary lines on the
current ice phase diagram.
ACKNOWLEDGMENTS
The use offacilities at the Institut Laue-Langevin, and
associated SERC funding for JLF and OVB, is gratefully
acknowledged. We thank W. Press for the advice in using his
program for refining rotationally disordered systems and E.
Whalley for some helpful comments on the interpretation of
his thermodynamic and dielectric work on high pressure
ices.
 Kuhs et a/. : Structure of ices VI, VII, and VIII
Ip. T. T. Wong and E. Whalley, J. Chern. Phys.64, 2359 (1976).
2p. Bames, D. V. Bliss, J. L. Finney, and J. E. Quinn, Faraday Discuss. R.
Soc. Chern. 69, 210 (1980).
3M. D. Morse and S. A. Rice, J. Chern. Phys. 76, 650 (1982).
4M. Townsend, S. A. Rice, and M. D. Morse, J. Chern. Phys. 79, 2496
(1983).
5D. Bloch, J. Paureau, J. Voiron, and G. Parisot, Rev. Sci. Instrum. 47, 296
(1976).
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J. Chern. Phys., Vol. 81, No.8, 15 October 1984
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