PRL 99, 016402 (2007)

PHYSICAL REVIEW LETTERS

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Why Is Polonium Simple Cubic and So Highly Anisotropic?

Dominik Legut,1,2,* Martin Friak,1 and Mojmr Sob3,1
Institute of Physics of Materials, Academy of Sciences of the Czech Republic, Zizkova 22, CZ-616 62 Brno, Czech Republic
2
Faculty of Chemistry, Institute of Materials Chemistry, Brno University of Technology,
Purkynova 118, CZ-612 00 Brno, Czech Republic
3
Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic
(Received 26 October 2006; published 6 July 2007)

Using the state-of-the-art ab initio electronic structure calculations, we explain why
-Po prefers the
simple cubic structure (it is due to the relativistic mass-velocity and Darwin terms), elucidate its extreme
elastic anisotropy (this is an intrinsic property of the simple cubic crystal structure), and predict a
transformation to a mixture of two trigonal structures at pressures of 13 GPa.
DOI: 10.1103/PhysRevLett.99.016402

PACS numbers: 71.15.Mb, 71.15.Rf, 71.55.Ak, 71.70.Ej

Introduction.Polonium is the only element on the

Earth that possesses the simple cubic (sc) structure, one
of the simplest crystal structures of all. It has the atomic
number Z
84 and is very rare and extremely radioactive,
at present known in 36 isotopes. The energy released by its
decay is very large, and hence polonium has attracted
attention for usage as a lightweight heat source for thermoelectric power in space satellites. It also can be mixed or
alloyed with beryllium to provide a flux of neutrons, used
for removing dust from photographic paper as well as for
eliminating the static charges in textile mills, and also as
the initiator of a chain reaction in atomic bombs constructed in the middle of the 20th century. Although polonium is so rare, it harmfully enters our lives, for example,
via air, soil [1], and plants such as tobacco [2], mushrooms
[3], and even tea [4].
In the ground state, solid polonium exhibits the sc structure (
-Po). Here the atoms are placed at the corners of a
simple cubic unit cell with the lattice parameter a


[5]. The second allotrope, -Po, has a rhombo3:345 A
hedral (trigonal) structure with the lattice parameter aR


and a rhombohedral angle of 98 130 [6]. This
3:359 A
structure may be derived from the sc structure of
-Po by a
small uniaxial distortion along the [111] direction (i.e., by
stretching the simple cubic cell along its body diagonal).
Both allotropes coexist in the temperature range of
1854  C  1:5  C [7].
Let us note that most metallic elements within the
periodic table have the body-centered cubic (bcc), the
face-centered cubic (fcc), or hexagonal close-packed
(hcp) structure. The former two structures may be continuously connected with the sc structure by means of socalled trigonal deformation path. This path is usually described by a parameter c=a, where c is measured along the
[111] direction and a is measured along a perpendicular
direction. If we ascribe the value of c=a
1 to the bcc
structure, then at c=a
2 we obtain the sc structure and at
c=a
4 the fcc structure; all other structures along the
path are trigonal [8]. Alternatively, the trigonal structures
along this path may be described by a rhombohedral unit
0031-9007=07=99(1)=016402(4)

cell characterized by the lattice constant aR and the angle

between two diagonals of the unit cell faces; this angle
equals 60 , 90 , and 109 280 for the fcc, sc, and bcc
structures, respectively.
Investigation of physical and chemical properties of Po
is very difficult due to its strong radioactivity and the
presence of the decay products. Most available experimental characteristics of Po have been collected in [9]. It turns
out that, to the best of our knowledge, no experimental
information on elastic behavior of polonium exists. It has
been suspected that the sc structure of Po could be due to
one of the relativistic effects, a strong spin-orbit coupling
[10], but this conclusion has not been supported by sufficient quantitative arguments. The main purpose of this
work is to explain the stability of the sc structure of
-Po
and its extreme elastic anisotropy.
Methods.At present, many physical and chemical
properties at or far from equilibrium are being predicted
within the framework of the density-functional theory [11].
State-of-the-art electronic structure calculations [12] provide understanding of matter at the atomic and electronic
scale with an unprecedented level of detail and accuracy.
With the help of such calculations, we can obtain information which is not accessible experimentally. For solids
consisting of atoms with higher atomic numbers, such as
lanthanides, actinides, and the elements of the 6th period,
relativistic effects must be included properly.
Results and discussion.The electronic structure of sc
Po was first calculated by Lohr [10] within the relativistically parametrized extended Huckel method, i.e., not from
first principles. The ab initio studies of the electronic
structure and elastic properties of Po were performed
only recently [1317]. In Ref. [13], the electronic structure
of Po was calculated by means of all-electron full-potential
linearized augmented plane waves method (FLAPW, the
WIEN97 code [18]). For exchange-correlation energy, both
local-density approximation [19] (LDA) and generalized
gradient approximation [20] (GGA) were employed and
elastic bulk modulus B as well as the tetragonal [C0

C11  C12 =2] and trigonal (C44 ) shear moduli were evaluated. Later, we included also the effect of relativistic spin-

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PHYSICAL REVIEW LETTERS

PRL 99, 016402 (2007)

orbit (SO) coupling and analyzed the impact of various

relativistic terms on electronic structure and total energy of
Po [14]. Kraig et al. [15] adopted the LDA pseudopotential
total energy scheme and evaluated the elastic moduli B and
C0 . Lach-hab et al. [16] used the LDA FLAPW method and
calculated the total energy of Po in a number of structures
as well as the elastic constants for the sc structure. In the
above two papers, however, the effect of the SO coupling
was not included in the first-principles calculations. Only
in Ref. [16], SO interaction was taken into account a
posteriori within the semiempirical tight-binding approach
fitted to the ab initio results. Further, neither [15] nor [16]
explained satisfactorily why Po exhibits the sc structure. In
[17], the SO interaction was reported to be the origin of the
sc structure of Po. However, these authors did not include a
large increase in the atomic volume of Po when the SO
interaction is incorporated (about 5% according to our
calculations see Table I). We found that the volume
change is critically important for the correct description
of sc Po. In this Letter, we perform detailed ab initio
electronic structure calculations of Po using the FLAPW
method (WIEN2K code [21]). An extended account of these
results may be found in [14]. The equilibrium atomic
volumes Veq and bulk moduli B of sc Po calculated without
and with the SO coupling using both LDA and GGA for
exchange-correlation energy term are given in Table I. It
may be seen that when the SO coupling is added, the
equilibrium atomic volumes are shifted by about 5%
higher. This is about twice as much as reported by Lachhab et al. [16], who found that the effect of the inclusion of
the SO coupling on the equilibrium atomic volume is only
about 2.5% in their semiempirical tight-binding approach.
The bulk modulus, on the other hand, decreases when the
SO coupling is included, which is connected with a higher
value of the lattice constant. Therefore, it may be concluded that the SO coupling should be included at the level
of first-principles calculations to get physically correct
results. Further, it may be seen from Table I that only the
GGA and LDA  SO calculations reproduce satisfactorily
the experimental equilibrium volume. As the effect of
SO coupling must be incorporated, in the following, we
will discuss mainly the LDA  SO findings.
Figure 1 shows the total energy profiles of Po calculated
within the LDA  SO along the trigonal deformation path
described above. As the sc structure is the ground state of
Po, the total energy along this path for the equilibrium
atomic volume (V=Vexp
0:99) exhibits naturally the
TABLE I. The ratios of the calculated equilibrium and experimental atomic volume Veq =Vexp and the bulk modulus B (GPa)
for sc Po using different approximations (see the text) without
and with spin-orbit (SO) interaction.
Approximation

GGA

GGA  SO

LDA

LDA  SO

Veq =Vexp
BGPa

1.01
46.9

1.06
40.1

0.94
57.1

0.99
42.3

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global minimum for this structure (c=a
2, ln c=a

0:693). The bcc structure (c=a
1, ln c=a
0) and the
fcc structure (c=a
4, ln c=a
1:386) have a considerably higher energy at the equilibrium atomic volume.
These structures exhibit symmetry-dictated extrema (maxima in this study) [8,22] of the total energy. We may
observe two other local minima that accompany the bcc
and fcc structures from the outer sides; these are not
dictated by symmetry. A similar curve was obtained earlier
in [13,15] without the inclusion of the SO coupling.
If the volume is increased the total energy profile preserves its shape exhibiting the lowest total energy for sc
structure as well as the maxima for bcc and fcc structures.
On the other hand, if the atomic volume is decreased, the
situation changes dramatically (see Fig. 1). For the atomic
volume V=Vexp  0:96, which corresponds to a relatively
low pressure of 2.6 GPa, the total energy profile becomes
flat around the sc structure and, for the lower atomic
volumes, the total energy of sc structure exhibits a maximum accompanied by two shallow local minima.
Therefore, at increased pressure, Po loses its sc structure
and becomes trigonal. This finding may be connected with
the fact that -Po, a higher-temperature allotrope of Po, is
also trigonal. It would be desirable to apply the pressure of
13 GPa and see whether
-Po becomes trigonal as well.
Figure 1 suggests that we could expect a bimodal mixture
of trigonal structures, one type exhibiting a value of c=a <
2 and the other type a value of c=a > 2. It may be supposed
that the structure with c=a < 2, resembling -Po found
experimentally, should be stable. The other structure with
c=a > 2 might be, in principle, unstable with respect to
some other deformation or phonon mode, but this analysis
is out of scope of this Letter. Let us note that the total
energy behaves similarly also in the case when the
SO interaction is neglected [13,14].
Now, let us ask what stabilizes the sc structure of Po at
ambient conditions, whereas its isoelectronic analogues,

FIG. 1. The total energy profiles of Po calculated within the

LDA with the SO coupling included along trigonal deformation
paths for various volumes studied. The energies are given
relative to the ground-state energy E0 . The full line with circles
shows the total energy of Po at equilibrium atomic volume
(V=Vexp
0:99).

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PHYSICAL REVIEW LETTERS

tellurium and selenium, have a less symmetric trigonal

spiral structure? Let us note here that the sc structure
may be considered as a special case of a trigonal spiral
structure [23]. Therefore to analyze this question, we have
calculated the electronic structure and total energy of
polonium in trigonal spiral tellurium structure and of tellurium in the sc structure. Initially we included all important relativistic effects, i.e., the Darwin term, mass-velocity
term, and SO interaction. Subsequently, we have employed
a nonrelativistic approach. The trigonal spiral tellurium
structure has more degrees of freedom than the sc structure
and, therefore, in addition to the volume, all these internal
parameters were fully relaxed. Our results show that in
relativistic calculations Po indeed prefers the sc structure.
The relaxation of initial parameters of the trigonal spiral
structure (e.g., experimental Te values [24]) has always
converged to those which correspond to the sc structure.
On the other hand, in the case of Te, the trigonal spiral
structure is stable and is favored by 0:6 m Ry=atom with
respect to the sc structure. The same trend was found when
the spin-orbit interaction was omitted and only the Darwin
and mass-velocity terms were included. However, when we
fully neglect the relativistic effects, i.e., both the Darwin
and mass-velocity terms as well as the SO interaction, the
situation in the case of Po reverses (Fig. 2). Now, the sc
structure of polonium lies by 0:3 m Ry=atom higher than
the relaxed trigonal spiral structure. However, Te still
prefers its ground-state trigonal spiral structure with respect to the sc one by 1:9 m Ry=atom. Therefore we may
conclude that it is not the SO interaction which is responsible for the sc structure of Po but the relativistic massvelocity and Darwin terms which reverse the structural
order in Po, but not in Te. Apparently, it is connected
with the fact that, in the series Se-Te-Po, the effect of the
mass-velocity and Darwin terms increases somewhat faster
than the effect of the SO-term [25]. Therefore, the impact
of the mass-velocity and Darwin terms outweighs the
influence of the SO term and has a predominant role in
determining the ground-state structure.

Another striking feature of the sc Po is its strong elastic

anisotropy. In all our calculations, the elastic anisotropy
factor [26] A
C44 =C0 is less than or equal to 0.17
(Table II, elastic isotropy corresponds to A
1). To the
best of our knowledge, there is no other solid with such a
low value of the elastic anisotropy factor. As with decreasing atomic volume the sc structure loses its stability with
respect to trigonal deformation (Fig. 1), the C44 and, therefore, also the elastic anisotropy factor goes to zero (Fig. 3).
Let us note here that the LDA  SO calculations converged very poorly in the region of pressures of 13 GPa
and, therefore, we do not know whether the square in Fig. 3
at pressure equal to 2.3 GPa indicates a deep minimum or if
it is an artifact of the calculation. Nevertheless, we may say
quite reliably that the trigonal shear modulus C44 (and,
therefore, also the elastic anisotropy factor A) vanishes for
a pressure in the interval 13 GPa. For comparison,
Table II displays the tetragonal and trigonal shear moduli
C0 and C44 as well as the elastic anisotropy factor A for
several solids with extreme elastic anisotropy [27]. Alkali
metals represent the other pole of the elastic anisotropy.
They exhibit the highest elastic anisotropy factors, up to
8.5 for Li (Table II).
It transpires from the analysis of the elastic properties
[27] that, except Po, all the materials with the lowest values
of the elastic anisotropy factor (A < 0:4) have the NaCl
structure which reduces to the sc structure when the atoms
become identical. This suggests that the extremely low
value of the elastic anisotropy factor A in both sc Po and
NaCl-structure compounds is induced by their crystalline
structure itself. Indeed, we can understand the low values
of A on the basis of the following considerations:
In an open structure such as sc or NaCl structure, we
may suppose that for elastic constants the behavior of the
first coordination shell will be dominant. Now, let us apply
the same uniaxial deformation along the [001] and [111]
axes, i.e., the tetragonal and trigonal deformation, respectively. In the coordination system where the loading axis is
the z axis, the corresponding deformation tensor is "

diag"=2; "=2; ", where " is the relative elongation
TABLE II. The calculated values of elastic anisotropy factor A
for Po as well as the extreme experimental values of A for
selected elements and compounds. All experimental values
were taken from [26]. The abbreviations are the same as in
Table I.
Material (method)

FIG. 2. The energy-volume curves of Te and Po in their ground

state and mutually reversed structures calculated when all relativistic effects were neglected. The trigonal spiral structures were
fully relaxed.

Po (LDA  SO)
Po (LDA)
Po (GGA)
Po (GGA  SO)
SnTe
RbBr
Nb
Li

016402-3

C0

C44

34.40
48.30
36.60
26.80
52.50
13.26
56.00
1.03

2.17
3.47
3.54
4.55
11.72
3.80
28.73
8.78

0.063
0.072
0.097
0.170
0.223
0.287
0.513
8.524

T (K)
0
0
0
0
300
300
300
298

Structure
sc
sc
sc
sc
NaCl
NaCl
bcc
bcc

PRL 99, 016402 (2007)

PHYSICAL REVIEW LETTERS

FIG. 3. The elastic anisotropy factor A
C44 =C0 for sc Po as a

function of pressure. Relativistic effects are included.

along the loading axis. The deformation energy per unit of

volume is 32 C0 "2 and 32 C44 "2 for tetragonal and trigonal
deformation, respectively. In the sc or NaCl structure, the
first coordination sphere consists of six atoms at  100
,
 010
, and  001
positions. When we perform the
tetragonal deformation, four nearest-neighbor bonds are
shortened by "=2 and two of them are elongated by ".
In the case of trigonal deformation, all bonds are elongated
by "2 =2. If no very strong angular forces are present (which
may be supposed in an sp-metal or in ionic materials with
the NaCl structure), then the elastic energy is proportional
to the squares of the changes of the lengths of bonds. For
tetragonal deformation, the changes of the lengths of bonds
provide a deformation energy proportional to "2 , but in the
case of trigonal deformation, the corresponding deformation energy is of the order of "4 , the quadratic term is
completely missing and, therefore, at least in this approximation, the C44 is zero. A small positive value of C44 in
these solids is then due to the effect of the second neighbors and/or weak angular forces which deliver a small
contribution to the deformation energy proportional to
"2 . Therefore, we may conclude that a very low value of
the elastic anisotropy factor in sc Po and in the compounds
with the NaCl structure is an intrinsic property of these
crystalline structures.
Conclusion.In conclusion, we were able, on the basis
of the state-of-the-art ab initio electronic structure calculations, to explain the stability of the sc structure of
-Po
(similarly as the yellow luster of gold [28], it is due to the
relativistic effects), to analyze its extreme elastic anisotropy (it is an intrinsic property of the sc crystal structure),
and to predict a bimodal mixture of trigonal structures of
Po at or above pressures of 13 GPa. We hope that our
theoretical results will stimulate corresponding pressure
experiments in the near future.
This research was supported by the Grant Agency of the
Czech Republic (Project No. 202/06/1509), the Grant
Agency of the Academy of Sciences of the Czech
Republic (Project No. IAA1041302), and by Research
Projects No. AV0Z20410507 of the Academy of Sciences
of the Czech Republic and No. MSM0021622410 of the
Ministry of Education of the Czech Republic.

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*legut@ipm.cz
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