ARTICLE IN PRESS

Journal of Physics and Chemistry of Solids 71 (2010) 357–363

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

First principles study of structural stability, electronic and

related properties of (NH4)2SO4
B. Andriyevsky a,b,n, K. Doll a, M. Jansen a
a
Max-Planck-Institute for Solid State Research, Heisenbergstrasse 1, D-70569 Stuttgart, Germany
b
Faculty of Electronics and Computer Sciences, Koszalin University of Technology, Śniadeckich Str. 2, PL-75-453 Koszalin, Poland

a r t i c l e in fo abstract

Article history: The electronic structure and related physical properties of crystalline ammonium sulfate, (NH4)2SO4,
Received 30 July 2009 have been studied using the first principles code CRYSTAL06 at the B3LYP level of theory. The title
Received in revised form compound has been found to possess one stable and three metastable configurations, all within the
4 November 2009
polar space group Pna21 (no. 33). Two of the metastable polymorphs are newly predicted and have not
Accepted 25 December 2009
yet been observed experimentally. The different configurations show considerably varying magnitudes
of the spontaneous polarization Ps. All coefficients of the elastic stiffness tensor, ckl, and elasto-electrical
Keywords: tensor, eki have been calculated for the first time and have been found to agree satisfactorily with
A. Inorganic compounds experimental data, as far as available.
C. Ab-initio calculations
& 2009 Elsevier Ltd. All rights reserved.
D. Elastic properties
D. Electronic structure
D. Ferroelectricity

1. Introduction permanent dipole moments of the NH4 groups. In [12], a

phenomenological theory based on an order parameter was
Crystalline ammonium sulfate (NH4)2SO4 undergoes a first- introduced; whereas other explanations were based on a soft
order ferroelectric phase transition at 223 K [1,2]. Characteristic mode behavior [13] or a reorientation of the complex group
properties are a relatively small value of the Curie-Weiss constant NH(1) (2)
4 –SO4–NH4 [14].
[3] and a peculiar temperature dependence of the spontaneous One of the most important properties of ferroelectric materials
polarization, which vanishes by cooling within the ferroelectric is the spontaneous polarization. Only a few years ago, a sound
phase and changes its sign at 85–87 K [4,5]. Such a complicated theoretical basis for the calculation of the spontaneous polariza-
temperature dependence of the spontaneous polarization has tion was given, by the modern theory of polarization [15].
been assigned to the existence of two nonequivalent ammonium According to this theory, the polarization is only defined as a
groups NH(1) (2)
4 and NH4 , giving non equal temperature dependent difference, and a quantitative description became possible. It is
contributions to the spontaneous polarization, which therefore thus one of the aims of this manuscript to compute properties
can be regarded as of ferrielectric type [5,6]. In both phases, four such as the spontaneous polarization, for the title compound.
formula units (NH4)2SO4 are in the unit cell [2,3,7,8]. The Besides, the influence of elastic distortions is studied, and
transition from the space group Pnam to Pna21, accompanied properties such as the piezo-electric response and elastic
with the loss of the mirror plane ab and of the center of symmetry, constants are computed.
leads to the occurrence of a spontaneous polarization along the
c-axes. Despite many previous investigations, the phase transition
mechanism in this crystal is still not well understood. Two 2. Method
different mechanisms have been suggested. The first one [9]
considers the changes in the strengths of hydrogen bonds the
In the present investigation, the first-principles LCAO code
driving force for the transition, while the second one [10,11]
CRYSTAL’06 [16] was used. A full geometry optimization was
suggests it to be a transition of order–disorder type due to the
performed and the E(V) curves were computed for various
configurations. Subsequently, the spontaneous polarization Ps,
n
bulk modulus B, coefficients of the elastic stiffness, ckl, (k, l = 1, 2,
Corresponding author at: Faculty of Electronics and Computer Sciences,
Koszalin University of Technology, Śniadeckich Str. 2, PL-75-453 Koszalin, Poland.
y, 6) and coefficients of the elasto-electrical tensor eik (i= 1, 2, 3)
Tel.: +48 943 478690; fax: + 48 943 433479. were calculated using the same approach as for the earlier study
E-mail address: [email protected] (B. Andriyevsky). of triglycine sulfate [17]. Ps, ckl, and eik have been calculated in the

0022-3697/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2009.12.090
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358 B. Andriyevsky et al. / Journal of Physics and Chemistry of Solids 71 (2010) 357–363

ab-initio approach for the first time. These calculations thus equation of state E(V) for this fourth configuration is shown in
complement previous experimental studies of the dielectric Fig. 1 (magenta curve). The total energy of this configuration at
properties [18]. the equilibrium is very close to the analogous energy for the
The calculations were done within the framework of the structure as33_2 (Fig. 1). In Fig. 1, all E(V) curves were fitted with
hybrid functional B3LYP for the exchange and correlation part of the Murnaghan equation of state [22],
the Hamiltonian. The basis sets were chosen as follows: for sulfur 8" #3 " 2 #2 " 9
   2=3 #=
a [4s3p1d] basis set (the inner [3s2p] shells as in [19], one more 9V0 B < V0 2=3 0 V0 3 V0
EðVÞ ¼ E0 þ 1 B þ 1 64 :
sp-shell with exponent 0.2413, and one more d-shell with 16 : V V V ;
exponent 0.383), for oxygen a [4s3p] basis set (the inner [2s1p]
shell as in [20], and two more sp-shells with exponents 0.4520495 ð1Þ
and 0.167888); for nitrogen a [3s2p] basis set (as in [21], A view of the b-planes of the different structures is shown in
but without d-shell); and for hydrogen a [2s] basis set (as in Fig. 2. Configurations as33_1, as33_2 and as33_3 are obviously
[21], but without p-shell). The H and N basis sets used correspond different. Although configuration as33_3 looks similar to as33_4,
to the original 6-31G basis set, whereas the oxygen and sulfur however, it has clearly different unit cell dimensions and is
basis sets are somewhat larger. A k-point sampling net of the size therefore different. Also, when computing the powder diffraction
4  4  4 was used. diagram with the code Diamond, (http://www.crystalimpact.
com), then the 4 structures have a different powder diffraction
diagram for the main peaks and their intensities, for angles
3. Results and discussion around 2y = 201. A method to test the stability of the newly
predicted phases would be to compute phonon frequencies and
The main part of the present study was the optimization search for imaginary frequencies. This is however not possible for
(relaxation) of the crystal structure. The starting point was the general k with the present CRYSTAL’06 release, and would also be
ammonium sulfate structure in space group Pnam (sequential very demanding due to the unit cell size.
notation 62, labeled as as62 in the following) [8] and two crystal Within space group Pnam, the structure possesses an addi-
structures in the space group Pna21 (sequential notation is 33, tional ab-plane of symmetry, which is perpendicular to the
labeled as as33_1 and as33_2 in the following) [7]. The latter two horizontal direction of Fig. 2, and, in this case, the sulfur and
structures in space group Pna21 correspond to the ferrielectric nitrogen atoms lie in this ab-plane of symmetry.
phase [6]. As it is shown in Fig. 1, a common tangent of E2(V) and E3(V)
The calculation of the potential curves of the atomic config- can be fitted (green line); or equivalently, the enthalpies
urations as62 (space group Pnam) and as33_2 (space group Pna21) H2(P) =H3(P) are equal for the corresponding pressure (inset in
was straightforward. The potential curve of configuration as33_1 Fig. 1) which is computed to be P= 1.36 GPa. This demonstrates
(space group Pna21) could only be computed up to a minimum that there is a pressure induced transition between the config-
volume. When a volume reduction DV= V V0 of more than urations as33_2 and as33_3.
DV/V0 =  0.03 was reached (where V0 is the volume at the Thus, as a first result, two new configurations of (NH4)2SO4 in
minimum in energy), the total energy E of the structure as33_1 space group Pna21 have been found. The existence of these new
dropped by DEE 0.2 eV (red arrow in Fig. 1), and a new configurations seems plausible due to the existence of three
structure was obtained. When compressing further and again different symmetry independent molecular groups: NH(1) (2)
4 , NH4 ,
expanding, a new potential curve was obtained, labeled as as33_3. and SO4. If we assume a fixed number of building units per unit
While computing the potential curve of configuration as33_3, cell, then the larger number of independent building units in spae
another discontinuity in the potential curve was found, associated group Pna21 supplies more degrees of freedom to create more
with another structure, labeled as as33_4. The corresponding than one variant of atomic configurations, compared to the case of

Fig. 1. Total energy E as a function of the unit cell volume V for the polymorphs as33_1, as33_2, as33_3, and as33_4 (all within space group Pna21). The unit cell contains 4
formula units, and the energy is thus for 4 formula units. In the inset, the pressure dependence of the enthalpy difference H3 (P)–H2(P), for the polymorphs as33_2 and
as33_3 is displayed.
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B. Andriyevsky et al. / Journal of Physics and Chemistry of Solids 71 (2010) 357–363 359

Fig. 2. Irreducible parts of the b-plane of the unit cell for four configurations, as33_1 (a), as33_2 (b), as33_3 (c), and as33_4 (d). The cell dimensions are given for the
optimized crystal structure. Sulfur—blue, oxygen—cyan, nitrogen—olive, hydrogen—black. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

Fig. 3. Total energy E as a function of the unit cell volume V for the structures as62 (Pnam) and as33_2 (Pna21).

Fig. 4. Calculated unit cell parameters a, b, and c as a function of the volume. Inset: experimental values of the unit cell parameters a, b, and c, as a function of the
temperature [2]. (For interpretation of the references to colour in this figure, the reader is referred to the web version of this article.)
 ARTICLE IN PRESS
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the space group Pnam with only two symmetry independent transition can be compared with the theoretical difference of the
molecular groups NH4, and SO4. electronic energies DE= 0.0547 eV of the crystal unit cell (again
Using the experimental data of the temperature dependence of per 4 formula units) between the minima of the volume
the molar specific heat cp = dE/mol/dT in the range from 50 to dependences E(V) of as62 and as33_2 (Fig. 3) and is in the same
290 K [2,23], we have approximated the change of the internal range.
energy by integration (inset in Fig. 3). The discontinuity near the From the computed crystal structures, which were fully
Curie temperature TC is of the order of 0.042–0.075 eV, per 4 optimized for various fixed volumes, the volume dependences of
formula units. This discontinuity at TC due to the ferroelectric the unit cell parameters a(V), b(V), and c(V) were obtained. They

Table 1
Spontaneous polarization Ps of the polar structures at the computed equilibrium volume Ve and for volumes Ve 7 10 A3.

Atomic configuration Ps at Ve  10 A3 (C/m2) Ps at Ve (C/m2) Ps at Ve + 10 A3 (C/m2)

of space group Pna21

as33_1  0.022  0.025  0.026

as33_2 0.012 0.012 0.011
as33_3  0.025  0.035  0.044
n)
as33_4  0.017 0.018 0.052

Fig. 5. Total energy E and double spontaneous polarization 2Ps vs. unit cell volume V for configuration as33_1.

Fig. 6. Total energy E and double spontaneous polarization 2Ps vs. unit cell volume V for configuration as33_2.
 ARTICLE IN PRESS
B. Andriyevsky et al. / Journal of Physics and Chemistry of Solids 71 (2010) 357–363 361

Fig. 7. Total energy E and double spontaneous polarization 2Ps vs. unit cell volume V for configuration as33_3.

Fig. 8. Total energy E and double spontaneous polarization 2Ps vs. unit cell volume V for configuration as33_4.

Table 2 Table 4
. Mulliken charges of the molecular groups SO4, NH4(1), NH4(2) for the configuration Bulk modulus B, elastic stiffness constants cij and bulk modulus Bv of ammonium
as33_1 in space group 33 (Pna21) (a= 7.8961 Å, b = 11.0998 Å, c = 6.6144 Å). sulfate with the symmetry of space group Pnam (in 109 N/m2).

Group parameter SO4 NH(1)

4 NH(2)
4
B Bv c11 c22 c33 c12 c13 c23 c44 c55 c66

qtot/e  1.52 0.78 0.75 Present 21.5 23.5 43.9 50.8 28.0 18.4 11.1 15.1 2.7 3.4 7.4
qS(N)/e 0.29  0.95  0.93 calculations
q4O(4H)/e  1.81 1.73 1.68 Experiment 21.5 21.7 35.2 29.7 36.0 14.1 15.7 17.3 9.5 7.0 10.3
[27]
Experiment 21.5 21.7 36.1 29.8 35.3 16.5 15.8 14.6 10.3 7.2 9.7
[28]
Experiment – – 35.6 28.1 36.3 – – – 9.3 7.5 9.9
Table 3 [29]
Mulliken charges of the molecular groups SO4, NH(1) (2)
4 , NH4 for the configuration

as33_2 in space group 33 (Pna21) (a= 8.3057 Å, b = 11.1990 Å, c = 6.1476 Å).

Group parameter SO4 NH(1)

4 NH(2)
4
are displayed in Fig. 4 together with corresponding experimental
temperature dependences a(T), b(T), and c(T) [2], extrapolated to
qtot/e  1.52 0.74 0.78 T=0 K (inset of Fig. 4). As the calculated lattice constants refer to
qS(N)/e 0.30  0.96  0.93
q4O(4H)/e  1.82 1.70 1.71
T=0 K, they should be compared with the corresponding
experimental values at the same temperature T= 0 K for both
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structures. If we take into account that the volumes above and 20%; or in the case of NaNO2 [33], the deviation of calculated and
below the phase transition are similar [2], then we can see that c experimental values of Ps is within a few percent. An uncertainty
becomes larger above the phase transition (i.e. in the as62 of the experimental value of Ps is usually caused by the absence of
structure), compared to the value of c below the phase transition, the corresponding experimental data at the temperature T= 0 K.
(i.e. in any of the ferroelectric phases as33_1, as33_2, as33_3, One however should take into account two points, which may
as33_4). This is in reasonable agreement with the experimental reduce the difference of the calculated and experimental absolute
result (see the inset in Fig. 4). Similarly, a becomes smaller above values of Ps. Firstly, the signs of Ps is positive for two configura-
the phase transition in the experiment, and in the present tions and negative for the two other configurations: with the unit
simulation. A reasonable agreement between experiment and cell arranged as in Fig. 2, the sign of Ps is positive for as33_2 and
theory is also found for b, when the extrapolation to T=0 K using a as33_4, but negative for as33_1 and as33_3. As it was already
quadratic polynomial approximation is taken into account. The mentioned, two polar atomic configurations, as33_1 and as33_2,
unit cell dimensions a, b, and c of the structures as33_3 and were found experimentally [7]. Because of the opposite signs of
as33_4 are clearly different, as can be seen in Fig. 4. This, together spontaneous polarization calculated for these configurations
with the corresponding difference of the total energies (Fig. 1), (Figs. 5 and 6) when arranged as in Fig. 2 and because of the
illustrates clearly that the structures as33_3 and as33_4 are two change of the sign of Ps(T) as a function of temperature [4,5], we
different structures. suggest that the low temperature phase of (NH4)2SO4
The spontaneous polarization Ps has been calculated for the (ToTC = 223 K) could be a mixture of the 4 polar configurations
four structures in space group Pna21 on the basis of the modern as33_1, as33_2, as33_3 and as33_4. Therefore, the total
Berry phase approach [15,24–25]. According to this approach, the spontaneous polarization of the crystal can be smaller than
spontaneous polarization Ps of a crystal is the sum of the the individual magnitudes of the spontaneous polarization of
electronic Pel and ionic Pion components [26], the configurations as33_1, as33_2, as33_3 and as33_4. Secondly,
Z Z the relative part of a certain configuration, among the four
! 1 !! ! ! !
Ps¼ dt d r j ð r ; tÞ ¼ P el þ P ion : ð2Þ mentioned above, changes with temperature. At relatively low
Vcell cell temperatures this part must be the greatest for the atomic
The results are displayed in Table 1 and Figs. 5 and 8. The configuration as33_2 possessing the lowest total energy E. As a
magnitudes of the polarization are different which confirms that result of this consideration and the data in Fig. 1 and Table 1, one
these are really four different structures. can expect that at a certain temperature T below the Curie
The results on the calculated spontaneous polarization in temperature TC = 223 K, the resultant spontaneous polarization Ps
Table 1 show that the absolute magnitudes of the spontaneous of the real crystal structure of (NH4)2SO4 may be equal to zero,
polarization Ps obtained are 2–5 times greater than the maximum which agrees qualitatively with experiment [4,5,27].
experimental value P(exp)
s E0.006 C/m2 [4,5,30]. This is a very As the configurations as33_1, as33_2, as33_3 and as33_4 in the
large deviation, and the spontaneous polarization in ferroelectrics ferroelectric phase have the same space group Pna21, it is possible
using the Berry phase approach is usually relatively close to the that these four crystalline structures could exist simultaneously.
experimental one; for instance, in the molecular crystal triglycine Then, if taking into account different values and signs of
sulfate, the computed value of the spontaneous polarization spontaneous polarization of these structures (Figs. 5–8), and a
Ps =0.035 C/m2 [17], is within the range of the experimental value, different ‘‘population’’ of the various structures as a function of
0.029–0.042 C/m2 [31,32], so that the corresponding deviation is temperature, one could expect a complicated temperature

Table 8
Table 5
Elastic-and-electric constants eik of ammonium sulfate for two configurations in
Elastic compliance constants sij (in 10  12 m2/N) and bulk modulus Br (in 109 N/m2)
space group Pna21 (in 10  3 C/m2).
of ammonium sulfate in space group Pnam.
e31 e32 e33 e24 e15
Br s11 s22 s33 s12 s13 s23 s44 s55 s66
Configuration as33_1  113  130  153  91.3 139
21.3 27.9 44.2 25.8  6.7  8.1  10.7 365 135 296
Configuration as33_2 76.9 13.3  226 505 0.02

Table 6
. Bulk modulus B, Bv and elastic stiffness constants cij of ammonium sulfate for two Table 9
configurations in space group Pna21 (in 109 N/m2). Piezo-electric constants dik of ammonium sulfate for two configurations in space
group Pna21 (in 10  12 C/N).
B Bv c11 c22 c33 c12 c13 c23 c44 c55 c66
d31 d32 d33 d24 d15
Configuration 12.1 15.3 38.7 38.5 22.6 12.6 3.8 2.7 8.1 4.8 10.8
as33_1 Configuration as33_1  1.51  2.44  6.32  11.3 28.7
Configuration 13.7 14.2 23.3 23.4 26.9 6.3 7.8 13.0 6.5 5.8 5.9 Configuration as33_2 5.96 6.08  12.8 78.0 0.004
as33_2 Experiment [26]  0 5.0  4.0

Table 7
. Elastic compliance constants sij (in 10  12 m2/N) and bulk modulus Br (in 109 N/m2) of ammonium sulfate for two configurations in space group Pna21.

Br s11 s22 s33 s12 s13 s23 s44 s55 s66

Configuration as33_1 13.5 29.2 29.1 45.8  9.2  3.9  1.9 124 206 92.1
Configuration as33_2 13.81 48.3 59.3 53.0  7.0  10.6  26.5 155 174 170
Experim. (130 1K) [12] 46 50 36
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dependence of the total spontaneous polarization. A Taking into account the different polar atomic configurations
superposition of different isomorphic crystalline structures with of the crystal, the agreement of the data obtained and the existing
a temperature dependent ‘‘population’’ within the ferroelectric experimental data for the constants dik is good.
phase would imply a displacement type of phase transition
rather than an order–disorder one. However, a simulation
of the temperature dependence is beyond the scope of this 4. Conclusions
article.
The computed Mulliken charges of SO4, NH(1) (2)
4 , NH4 for the
The first principles code CRYSTAL’06 has been applied
configurations as33_1 and as33_2 (space group 33, Pna21) are
successfully to the study of the equation of state E(V) of the
presented in Tables 2 and 3. The Mulliken charges are similar for
ferroelectric crystal (NH4)2SO4.
both cases and confirm essentially an ionic picture, with SO4 being
Four isomorphs of (NH4)2SO4 have been found in space group
close to a formal charge of  2, and similarly NH4 being close to +1.
Pna21, in which the crystal is ferroelectric. Only two of these
For the optimized crystal structure of (NH4)2SO4 the coeffi-
configurations are known experimentally so far, and it would be
cients of the elastic stiffness tensor cij (i, j = 1,2,y,6),
X very interesting to experimentally investigate the existence of the
si ¼ cij ej ; ð3Þ two new predicted configurations. The spontaneous polarization
j for these different atomic configurations has a very different
and the bulk modulus B, magnitude. This agrees qualitatively with the corresponding
experimental data on the characteristic temperature dependence
@P @2 E of the spontaneous polarization of the crystal, which changes sign
B ¼ V ¼V 2; ð4Þ
@V @V as a function of temperature.
have been calculated using the approach presented in [26]. For The spontaneous polarization, and all components of the
the calculation of one coefficient of the elastic stiffness tensor cij elastic and elasto-electric tensors of the crystal have been
or bulk modulus B, seven distortions in the range from 3% to 3% calculated from first principles for the first time, and a good
were applied. All the coefficients of the elastic stiffness cij and agreement with the existing experimental data was found.
elastic compliance tensors sij of (NH4)2SO4 have been calculated
for the structure with space group Pnam and two structures with
space group Pna21, respectively (see Tables 4–7). References
For the crystal configurations as33_3 and as33_4 of ammo-
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[28] V.S. Haussühl, Acta Cryst. 18 (1965) 839–842.
The corresponding piezo-electric constants dik (Table 9) were [29] A. Yoshihara, T. Fujimura, K.-I. Kamiyoshi, J. Phys. Soc. Jpn. 44 (1978)
calculated using Eq. (7) and the components of elastic compliance 1241–1247.
sik calculated before, [30] T. Yamaguchi, T. Tomita, N. Ikarashi, Ferroelectrics 169 (1995) 173–178.
[31] J. Stankowski, A. Galezewski, S. Waplak, U. Gruszczynska, H. Gierszal,
Ferroelectrics 6 (1974) 209–214.
X [32] K. Imai, J. Phys. Soc. Jpn. 49 (1980) 2263–2269.
dik ¼ eil slk ; i ¼ 1; 2; 3 k; l ¼ 1; 2; . . .; 6: ð8Þ [33] F. Ishii, T. Oguchi, J. Phys. Soc. Jpn. 71 (2002) 336–339.
l [34] R. Hill, Proc. Phys. Soc. London Sec. A 65 (1952) 349–354.