Copyright © 2013 by American Scientific Publishers Materials Focus

All rights reserved. Vol. 2, pp. 309–315, 2013

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Chemical Bonding and Single Crystal

Growth of ADP Crystals
Xiue Ren1 , Congting Sun1, 2 , Keyan Li1 , Dongli Xu1 , and Dongfeng Xue1, 2, ∗
1
School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China
2
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, P. R. China

ABSTRACT
From the viewpoint of chemical bonding, we show that the oriented distribution of chemical bonding of H2 PO4−
ion can dominate the growth of ammonium dihydrogen phosphate (ADP) single crystals. The effective distribu-
tion coefficient of chemical bonding is proposed to describe the modification of chemical bonds between growth
units during crystallization process, which is the intrinsic origin of morphology evolution of ADP crystals under
different pH values. From both theoretical calculations and experimental observations, we demonstrate that the
growth of ADP crystals along the a- and b-directions depends on the chemical bonding conditions of hydrogen
bonds between H2 PO4− groups during the crystallization, which leads to the morphology transformation of ADP

ARTICLE
from the podgy to slender under different pH values.
KEYWORDS: ADP, Chemical Bonding, H2 PO4− Groups, pH Values.

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1. INTRODUCTION
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Copyright: American Scientific Publishers interface. In this theory, the rela-
Fundamental studies have shown that crystal morphology
is a synergetic result of crystal structure and specific
growth conditions.1–5 Advanced functional inorganic mate-
rials with well-tailored morphologies have been fabricated
by selecting proper growth parameters, such as solvent,
additives, reaction time, and pH value.6–8 Efforts have
been made in order to exquisite control the nucleation
and growth during the crystallization process.9 10 Directly
probing the structural dynamics at the single atom level
is still beyond the capability of the present experimen-
tal techniques. Therefore, the combination of theoretical
calculations and experimental observations can provide a
more comprehensive understanding of the growth process
of single crystal.
The understanding of crystal shape develops from a
simple phenomenological description at the macroscopic
level to more microscopic intermolecular interactions.
Many efforts have been paid to relate the underlying
growth mechanism associated with habit modification to
the geometric characteristics, surface free energy and
intermolecular interactions, respectively.11–13 Recently, the
chemical bonding theory of single crystal growth has been
proposed to describe the crystal growth process and pre-
dict the growth morphology of inorganic crystals from
∗
Author to whom correspondence should be addressed.
Email: dongfeng@ciac.jl.cn
Received: 1 March 2013
Accepted: 12 March 2013
the Oct
viewpoint of chemical bonding between constituent
2015 04:45:51 14
units at the growth
tive growth rate Rhkl of the particular (hkl) crystal face
is directly proportional to the bond valence sum per unit
volume along the crystallographic orientation. This model
was well applied to predict the ideal morphology of inor-
ganic crystals within seven crystal systems and the mor-
phology evolutions of oxide crystals at different growth
environments, including pH values and additives.15–17 The
agreement between the calculations and experiments indi-
cates that the concept of chemical bond captures the main
interaction and can be utilized for the description of crys-
tal growth anisotropy. Constituent chemical bonds are thus
emphasized to understand crystal growth. In order to fur-
ther describe the role of chemical bonding interactions in
crystal growth, bond valence can reflect the localized inter-
actions between neighboring atoms and show the distribu-
tion of valence electrons of atoms along special direction
in crystallographic frame.18 19 In this work, ammonium
dihydrogen phosphate (ADP) is selected as an example for
studying crystal growth behaviors from solution because
ADP crystals are easy to growth and possess high crys-
tal perfection.20 21 Under ambient conditions, ADP crystal-
lizes in the tetragonal system with space group I 4̄2d and
exhibits a tetragonal prism consisting of four (100) faces
terminated by two opposing tetragonal pyramids (101)
faces. The crystal morphology of ADP single crystal was
constructed on the basis of the effective contribution of
chemical bonding conditions per growth unit along differ-
ent crystallographic directions. Under different pH values,

Mater. Focus 2013, Vol. 2, No. 4 2169-429X/2013/2/309/007 doi:10.1166/mat.2013.1085 309

 Chemical Bonding and Single Crystal Growth of ADP Crystals Ren et al.

H2 PO4− and H3 PO4 can generate different aggregations,
including H2 PO4− , H4 (PO4 22− , and H5 (PO4 2− , the chem-
ical bonding conditions of which dominate the growth
morphology of ADP crystals. The calculated morpholo-
gies of ADP crystals are in a good agreement with our
experimental observations, confirming the dominant role
of chemical bonding during the growth process.
2. THEORETICAL BASIS
Crystal growth can be considered as the forming and
breaking of bonds between crystallizing particles such
as atoms, ions or molecules. When the crystal crystal-
lizes from a growth system, the growth units gradually
come close together by the interactions with neighboring
atoms and enter the crystal lattices along special bond-
ing directions. The crystallization driving force at the
growth interface is directly proportional to the chemical
bonding capability per molecule. Therefore, growth habits
of crystalline materials depend on the detailed crystallo-
graphic structure and bonding interactions between con-
ARTICLE
length of 1.414 Å occur between two adjacent PO4 groups,
which are perpendicular to the c-axis. Therefore, the
anionic phosphate groups bonded together by a 3D bond-
ing network dominate the crystal chemistry of ADP. When
ADP crystallizes from the solution, the bonding interac-
tion between H2 PO4− and adjacent ions is the dominant
factor for the crystallization process. H2 PO4− groups are
selected as central ions. When central ions incorporate into
the crystal lattice, the bonding number N of each central
ion with symmetry equivalent positions is constant. The

total chemical bonding capability i Ni × si per molecule
is determined by the Brown’s Rules of Valence.18 Accord-
ing to the symmetry operators within the crystallographic
frame, the chemical bonding capability contributions per
molecule are therefore quantitatively apportioned between
the interplanar and internal planes and written as
  
Nti × si + Nni × si = Ni × si (1)
i i i
where Nti is the total number of i type bonds per molecule
within a selected slice, Nni is the total number of i type

stituent units (Fig. 1). And then the characteristics of

chemical bonding in crystallographic frame are taken as bonds per molecule between two adjacent slices, si is the
an important starting point. For ADP, the crystal is con- bond valence of the i-type bond.
structed by chemical bonding between two fundamental The distributions of the bonding capability per molecule
+
units of H2 PO4− and NH
Delivered
4 . All chemical bonds formed between the interplanar and internal planes are different for
by Publishing Technology to: Northeastern University Campus
between constituent units can be classified into three types each selected slice, which leads to the anisotropy of crystal
IP: 50.50.154.8 On: Sat, 17 Oct 2015 04:45:51
by their bond lengths and orientations Copyright:
(Fig. 2). American growth. Publishers
The first Scientific Therefore, a complete treatment of the growth of
kind of chemical bonds labeled as  bonds are HN  −O crystal face should include contributions not just from the
covalent bonds with a longer nitrogen-to-oxygen length bulk and surface of crystals, but also from the edges and
of 3.169 Å, which expand along the c-axis. The sec- corners. Assuming that crystal surface has the structure of
ond kind of chemical bonds noted as  bonds are also bulk crystal allows us to get a simple relation between the
HN  −O covalent bonds with a shorter nitrogen-to-oxygen chemical bonding contribution per molecule for the forma-
length of 2.915 Å, which are approximately parallel to tion of slice and its relative position in the corresponding
the ab plane. Both of them are formed between H2 PO4− slice. For example, when one molecule is situated in face,
and NH4+ ions. However, the last ones represented by edge, or corner of a slice, the effective contribution of this
 bonds (i.e., the HO   O hydrogen bonds) with bond molecule is reduced to 1/2, 1/4, or 1/8. Hence, the effective

2
Interface

2
Bulk crystal

1 3

1 3

Bulk crystal Interface

(a) Microscopical characteristics (b) Macroscopical morphology

Fig. 1. The relationship between of chemical bonding characteristics and crystal growth habit. Number 1, 2 and 3 describe the discrepancies in
chemical bonding conditions of growth unit situated in bulk crystal and interface, which further lead to anisotropy of crystal growth.

310 Mater. Focus, 2, 309–315, 2013

Ren et al. Chemical Bonding and Single Crystal Growth of ADP Crystals

α Bond
H β Bond Chain a (b)
N
O
P c
β Bond

γ Bond

γ Bond Chain a (b)

α Bond Chain

Fig. 2. Schematic drawing of chemical bonds formed between constituent units for ADP crystals.  bonds are HN  −O covalent bonds with a longer
nitrogen-to-oxygen length of 3.169 Å,  bonds are also HN  −O covalent bonds with a shorter nitrogen-to-oxygen length of 2.915 Å,  bonds are the
HO   O hydrogen bonds with bond length of 1.414 Å.


contribution i Ni∗ × si per molecule may be expressed The
criterion is thought as an important habit factor to

ARTICLE
as an average of contributions from the face, edges and reflect the normal growth rate of every plane, that is, the
corners, then planes having smaller
values may emerge at the end
 of growth while the planes having bigger
values vanish
 ∗  face  edge
Ni × si = Delivered
Ni ×by si + N
Publishing
i × s
Technology
i
finally. According to the structural dominance of central
to: Northeastern University Campus
i i i
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and2015
their04:45:51
sensitivity for environments, the discrepan-
 
Copyright: American cies in chemical
Scientific bonding can be obtained. Therefore,

Publishers
 
+ Nicorner × si fj (2) can describe the shape evolution of crystalline materials.
i j

fj is the right weight factor of the growth unit j in a

3. EXPERIMENTAL SECTION
selected slice, which is determined by its corresponding
position in the assigned slice. Eq. (1) can be rewritten as All reagents used in this experiment were from analyt-
 ∗   ically pure chemicals. In a typical preparation process,
Nti × si + Nni∗ × si = Ni ∗ × si (3)
i i i
ADP powders, deionized water and appropriate propor-
  edge  tion of phosphoric acid (or ammonia) were mixed in a
where i Niface , i Ni and i Nicorner are the number of 100 ml beaker. This mixture was transferred into a water
i type bonds situated in face, edge, and corner of a selected bath crystallizer at the constant temperature of 46.5  C
slice, respectively. with continuously stirring for 2 h, and then the solution
For most practical crystal growth, the system is often with excess solute was maintained for a period of 12 h at
far from ideal conditions. The bonding process between the same temperature. The saturated solution with differ-
constituent units is easily affected by the external environ- ent pH was obtained by taking 30 ml the upper transpar-
ments. For example, the weaker chemical bonds between ent liquid. After overheated at 75  C for 3 h, the solution
growth units, such as  hydrogen bonds between two adja- was naturally cooled down to the saturated temperature.
cent PO4 groups, are sensitive for the acid environment By addition of 5 ml 75% (v/v) ethanol-water mixture the
and exist as various phosphorous acid anions under dif- ADP crystallites were grown spontaneously under suffi-
ferent pH.22 This modification affects the local bonding ciently mixed condition and then were allowed to grow for
environment of growth units, that is, the net increase Ni∗ 2 min. Finally, the crystallites were collected by a pipette
of chemical bonds formed during crystallization process. and instantly dried by filter papers for further characteri-
Herein, a new parameter
, which is called as the effec- zation. The residual liquid was used for the measurement
tive distribution coefficient of chemical bonding, is intro- of pH. The solubility of ADP in solution with different pH
duced as a measure for the relative change of bonding was determined by traditional weight analysis. The mor-
interactions, and given by phology and size of all ADP crystallites were character-

Nni∗ × si ized directly using scanning electron microscope (SEM,

= i ∗
(4)
i Ni × si
JSM-5600LV, JEOL) measurements.

Mater. Focus, 2, 309–315, 2013 311

 Chemical Bonding and Single Crystal Growth of ADP Crystals Ren et al.

(A) (B) (C)

(D) (E) (F)

(G) (H) (I)

ARTICLE

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Copyright: American Scientific Publishers
(J) (K) (L)

Fig. 3. SEM images of ADP crystallites in solution with different pH values: (A) pH = 6.42; (B) pH = 6.05; (C) pH = 5.65; (D) pH = 4.68;
(E) pH = 4.24; (F) pH = 3.97; (G) pH = 3.83; (H) pH = 3.65; (I) pH = 3.43; (J) pH = 3.30; (K) pH = 1.64; (L) pH = 1.15, scale bar = 200 m.

4. RESULTS AND DISCUSSION a significant change, from the quasi-octahedron to slender,

The batch crystallization of ADP from the saturated solu-
tions with different pH values was performed by intro-
ducing the ethanol-water mixture. The necessary driving
force for crystallization or supersaturation is established
by the ethanol-water mixture to extract the solvent water.
Since the amount of ethanol-water is invariable at dif-
ferent pH, the influence of ethanol-water on the growth
rate of crystal faces will not be considered here. Well-
developed crystallites were obtained from the solution and
shown in Figure 3. It can be clearly seen that ADP crys-
tals show a high sensitivity to pH. Especially, the habit
of ADP crystallites at pH = 642 424 343 and 1.15 rel-
ative to the natural habit at stoichiometric value 3.83 has
and then to the quasi-octahedron again with decreasing
pH from 6.42 to 1.15. The curves of solubility of ADP
in solution with the different pH at 46.5  C are obtained
in Figure 4, which indicates that the solution concentra-
tion rapidly increases with the deviation of pH from the
stoichiometric solution. This wide variety of the solution
concentration is ascribed to the anion-anion interaction
in aqueous solution,25 which leads to the anisotropy of
growth rates. Furthermore, the addition of phosphoric acid
(or ammonia) to tune pH of the saturated solution directly
alters the proportion of various phosphorous acid anions,
which generates a substantial range of possible associates.
According to Raman spectroscopy studies,22–24 the forma-
tion of hydrogen-bonded phosphate associates (H5 (PO4 2−

312 Mater. Focus, 2, 309–315, 2013

Ren et al. Chemical Bonding and Single Crystal Growth of ADP Crystals

toward the associates H4 (PO4 22− and H5 (PO4 2− .25 26 It

180
is to be expected that similar equilibriums also hold
160 for ADP saturated solution. According to the theoretical
Solubility g/100g water

method proposed, the differences in the bonding interac-

140 tions between constituent units lead to the shape evolution
of crystals. Therefore, these anionic species are responsi-
120
ble for the evolution of growth rate of every crystal plane
and cooperatively give rise to the pH-dependent growth
100
behaviors of ADP crystallites, as shown in Figure 5.
80 In the stoichiometric solution of ADP, it has been
expected that most of phosphorous acid anions (H2 PO4− 
60 exist as monomers.27 H2 PO4− ions as dominant growth
units enter the crystal lattice, which need form four
1 2 3 4 5 6 7
 bonds, four  bonds and two  bonds during the
pH
whole crystallization process. The habit of ADP crystal-
Fig. 4. Effect of pH on the concentration of ADP saturated solution at lites inclines to the podgy. With tuning the solution pH
46.5  C. The stoichiometric value 3.83 is highlighted by a red circle. from 3.83 to 3.43, the concentration of ADP saturated
solution increases largely. This accelerates the dimer pro-
and H4 (PO4 22−  is susceptible to occur in solution con- cess of H2 PO4− monomers and benefits for the increase
taining H2 PO4− . These associates are expected to have of the content of H4 (PO4 22− dimers. Since H4 (PO4 22−
various similar atomic configurations in solution. Each of ion is a cluster of two phosphate groups bonded together

ARTICLE
them may exist in equilibrium with each other, the succes- through two  hydrogen bonds, they also can incorporate
sive dissociation and complex equilibriums in solution are into the crystal lattice as growth units and hold the sim-
proposed as follows: ilar chemical bonding to H2 PO4− ions. Nevertheless, in
the bonding process of H4 (PO4 22− ions, there exists the
H3 PO4  H+ + H2 PO4− (5) H4 (PO4 22− ion in order to
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− + IP: 50.50.154.8 On:
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2−
(6)Sat, 17
formOct 2015 
another 04:45:51
bond with adjacent phosphate groups, and
Copyright: American Scientific
then the Publishers
net increase of chemical bonding is four  bonds
H2 PO4− + H2 PO4−  H4 PO4 22− (7) and four  bonds. The two typical bonding processes are
H2 PO4− + H3 PO4  H5 PO4 2− (8) schematically given in Figure 6.
The effective distributions of chemical bonding per
It is obvious that the chemical equilibriums in Eqs. (5) molecule between the interplanar and internal planes for
and (6) move to the left side with decreasing pH, which different crystal faces in ADP crystals can be calculated
implies a tendency for the complex reaction to progress by Eqs. (2) and (3). Furthermore,
values of both typical

A B

pH = 6.42

pH = 3.83

pH = 3.43

pH = 1.15

Fig. 5. Scheme of the detailed effects of pH on the characteristics of anionic species in solution, and further on the morphology evolution of ADP
crystallites. (A) Experimental observations under the corresponding conditions taken from Figure 3. Theoretical growth forms of ADP crystallites.
(Double blue arrows indicate the inhibiting impacts brought by the inhibitors on the {101} faces, which leads to the relative expansion of {100} faces
represented by brown arrows.)

Mater. Focus, 2, 309–315, 2013 313

 Chemical Bonding and Single Crystal Growth of ADP Crystals Ren et al.

NH4+

H2PO4−

γ hydrogen bond

ΔNγ = 2

ΔNγ = 0

(1) (2) (3) (4)

ARTICLE

Fig. 6. Schematic representation of the habit evolution of ADP crystallites under different chemical bonding conditions between central H2 PO4−
anions: (1) central H2 PO4− anions existing as monomers and dimers in growth solutions, respectively; (2)  hydrogen chemical bonding between
central H2 PO4− anions ( N : the net increase of  hydrogen bonds); (3) chemical bonding of central H2 PO4− anions in crystal lattice; (4) growth
habits of ADP crystallites obtained by theoretical calculation.
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bonding processes were also obtainedIP: by
50.50.154.8
Eq. (4) andOn: Sat, 17
listed OctI. 2015
Table 04:45:51
Calculated
values of different crystal planes of ADP single
in Table I. The calculated results showCopyright: American
that {100} and Scientific
crystal. Publishers
{101} planes are still predominant for ADP crystals under Growth unit (hkl) plane
hkl
hkl /
100
two conditions, while their morphological importance has
−
a significant change. When H2 PO4− ions as dominant H2 PO4 (100) 0.389 1
(101) 0.360 0925
growth units incorporate into the crystal lattice, the distri-
 (001) 0.610 1568
bution i Nni ∗ within {101} planes is smaller than that (110) 0.780 2
of {100} planes. It means that {101} planes have a larger (112) 0.610 1568
morphology importance and finally the habit of ADP crys- H4 (PO4 22− (100) 0.332 1
2− (101) 0.417 1256
tallites inclines to the podgy. When H4 P2 O8 dimers enter
(001) 0.667 2009
the lattice site, the reform of hydrogen bonds in the ab (110) 0.665 2003
plane retards the growth along the a- or b-directions. (112) 0.667 2009
Therefore, the
value for {100} planes decreases and cor-
respondingly increases for {101} planes, which leads to
the transition of crystal habits from the podgy to slen- In contrast, anionic species H5 (PO4 2− can more readily
der with decreasing pH from 3.83 to 3.43. The theo- adsorb onto this surface. Moreover, the steric conformation
retical predictions obtained are well consistent with the of H5 (PO4 2− ion is similar to that of the two-phosphate
observations. cluster expected for the pure ADP growth, therefore, they
When the pH value further decreases to 1.15, there would have a comparative ability to occupy the sites
is an amount of phosphoric acid in high acid solution, of growth units through the hydrogen bonding interac-
which would be favored to form H5 (PO4 2− ions accord- tions with the exposed O-H bonds. These that act as
ing to the chemical equilibrium in Eq. (8). Since there inhibiting agents are known to preferentially adsorb in
exist the differences in the charge and stoichiometry the active sites (such as corner or ledge sites) of (101)
between H5 (PO4 2− and H4 (PO4 22− , H5 (PO4 2− ions as surface more strongly than others. Consequently the nor-
inhibitors have an influence on the growth habit. In terms mal growth of {101} planes would be slowed. However,
of the characteristics of surface structure of ADP crys- when pH increases to 6.42, although there are some lim-
tals in aqueous solution,27 the positively charged {101} ited HPO42− ions available in the solution, the effect of
+
surface with only NH4 ions provides a large barrier to HPO42− ions is relatively pronounced in view of the higher
the adsorption of positively charged metal ion impurities. charge than that of H5 (PO4 2− ions. Therefore, both of

314 Mater. Focus, 2, 309–315, 2013

Ren et al.
them will possess the similar growth behaviors and finally
lead to the formation of quasi-octahedron.
5. CONCLUSION
The morphology-chemical bonding relationships were
studied through a combination of the controllable growth
of ADP crystals under different pH values and chemical
bonding calculations. On the basis of the chemical bond-
ing interactions between constituent units, we calculate the
morphology evolution of ADP crystals from the podgy to
slender with decreasing pH values, in agreement with the
experimental observations. The underlying mechanism can
be ascribed to different chemical bonding conditions of
hydrogen bonds between H2 PO4− groups before they incor-
porate into the lattice under different pH values, which can
retard the growth along the a- or b-direction. The present
work further deepens our understanding of the morphol-
ogy evolution of crystal materials from the viewpoint of the
chemical bonding conditions of the growth units.
Acknowledgments: Financial support from the
National Natural Science Foundation of China (grant
nos. 51125009, 50872016 and 20973033), National Nat-
ural Science Foundation for Creative Research Group
(grant nos. 20921002 and 21221061)
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Talents Program of Chinese Academy of Sciences
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acknowledged.
Copyright: American Scientific
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