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Perovskites: Temperature and

Coordination Dependent Ionic Radii
a b
V. L. Miller & S. C. Tidrow
a
Department of Chemistry , Montgomery College , Rockville ,
Maryland , 20850
b
Department of Physics and Geology , The University of Texas – Pan
American , Edinburg , Texas , 78539
Published online: 07 Dec 2013.

To cite this article: V. L. Miller & S. C. Tidrow (2013) Perovskites: Temperature and Coordination
Dependent Ionic Radii, Integrated Ferroelectrics: An International Journal, 148:1, 1-16, DOI:
10.1080/10584587.2013.851576

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 Integrated Ferroelectrics, 148:1–16, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2013.851576

Perovskites: Temperature and Coordination

Dependent Ionic Radii

V. L. MILLER1 AND S. C. TIDROW2,∗

1
Department of Chemistry, Montgomery College, Rockville, Maryland 20850
Downloaded by [University of Newcastle (Australia)] at 08:15 03 September 2014

2
Department of Physics and Geology, The University of Texas – Pan American,
Edinburg, Texas 78539

Materials LaAlO3 and A2+TiO3 , where A is Ba, Ca, Pb and Sr, have been investigated
in order to determine the “effective” temperature dependent ionic radii of 12-fold
coordinated Ba2+, Ca2+, Pb2+, Sr2+ and La3+, and, 6-fold coordinated Al3+, Ti4+ and O2−
within the “simple” “ideal” cubic Perovskite structure. The recently developed planar
and volume constrained Perovskite model, which incorporates thermal expansion, has
been utilized to determine ionic radii values. As compared with Goldschmidt based
models, the newly determined radii provide significant improvements for more precise
modeling of the lattice parameter of Perovskites at room temperature as well as over
extended temperature ranges.

Keywords Temperature dependent ionic radii; Perovskite; structural phase transitions;

lattice modeling

Introduction
Society is confronted with a wide range of challenges, especially as related to sustainable
growth in both population and standard of living, which can be addressed through the
development of new materials. Models that accurately predict material properties can be
used to reduce the time and cost of discovering and developing affordable materials with
properties that outperform materials in current technologies as well as that provide novel
properties upon which new technologies can be derived to address a wide range of challenges
that society confronts.
Historically, the ionic radii model [1–3] and the modified ionic radii model through
coordination dependence [4–5] have provided reasonable, although limited, methods for
predicting whether a certain material will form. In addition, these models have provided
the ability to predict some limited physical properties of formed materials. For instance, in
the area of Perovskite materials, Goldschmidt’s efforts [3] in the first half of the twentieth
century resulted in a semi-empirical relationship, Goldschmidt’s tolerance factor, that is
still used to date for estimating whether a Perovskite material will form and whether it will
be cubic or distorted. Further, Goldschmidt’s formalism has been used to estimate the lattice
parameter of formed Perovskite materials using room temperature coordination dependent
ionic and crystal radii values [4, 5].

Received December 9, 2012; in final form August 25, 2013.

∗
Corresponding Author. E-mail: sctidrow@utpa.edu

1
 2 V. L. Miller and S. C. Tidrow

Perovskite materials are of technological interest since the Perovskite structure sup-
ports one of the largest, if not the largest, range of material properties of any material
classification found in nature. For instance, the wide range of atomic substituents that can
be utilized in the Perovskite crystal structure provide fill factors that theoretically range
from about 0.52 to 0.76 [6] in the “simple” “ideal” cubic Perovskite. Even higher and lower
packing densities are possible through multi-elemental substitutions on the structural sites
which form “ideal” cubic as well as non-cubic Perovskite solid solutions. Here, within this
paper, the term “simple” means that only one single element resides on a particular site in
the Pervoskite structure, i.e. no mixing or solid solutions, and the term “ideal” means cubic.
The large range of packing densities and the wide variety of substituents that change the
polarization per unit volume[6] and the band structure when incorporated in the Perovskite
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structure result in the enormous range of material properties [7] including, but not limited to,
catalytic, conductor, dielectric, electromagnetorestrictor, electro-optic, ferroelectric, ferro-
magnetic, magnetorestrictor, paraelectric, piezoelectric, pyroelectric, semi-conductor, and
superconductor.
Although numerous compounds with the general formula ABC3 form the Perovskite
structure [7], only a relatively small fraction of all Perovskites have the ideal structure at
room temperature [7]. The Perovskite structure may, depending upon atomic substitution,
take on any one of numerous crystallographic structures [8] at room temperature and the
ordered, double Perovskite structure, again depending upon atomic substitution, may take
on an even larger number of crystallographic structures [9] at room temperature. In both
cases, the ideal Perovskite is the less common structure [7]. A significant number of non-
cubic Perovskite compounds at room temperature transform into the simple ideal, ideal and
ideal ordered Perovskite at elevated temperatures [7, 10–12].
Recently [6], Goldschmidt’s formalism was revisited in an effort to construct a model
that improves our ability to a priori predict the formation of Perovskite materials as well
as a priori specify various material properties including, but not limited to, temperature
dependent lattice parameters, dielectric constants, and both volume and polarization induced
structural phase transitions of Perovskite materials. In that work, five planar constraints
and volume restrictions physically imposed on the simple ideal Perovskite structure were
compared with Goldschmidt’s tolerance factors through a newly introduced transformation
and mapping into ionic radii space [6]. As alluded to by Tidrow [6], ionic radii space can be
used to model various crystal structures and multi-site substitution onto each crystal lattice
site. The results of utilizing ionic radii space to begin modeling of the simple ideal Perovskite
structure are summarized below. Further, the ionic radii space construct is extended to
illustrate that presently available room temperature coordination dependent crystal radii of
Shannon consistently overestimate the lattice or volume parameters of Perovskite materials.
Next, coordination dependent ionic radii are reinvestigated and evaluated within the simple
ideal Perovskite constraint model to include temperature variation of ionic radii through
fitting temperature dependent lattice parameters of 25 simple ideal Perovskite materials
containing 25 different coordination dependent ionic radii with values for 8 of those ionic
radii presented in this paper.

Ionic Radii Space

Ionic radii space as shown in Fig. 1 is an expanded view from that of Tidrow [6] in order to
magnify the region where ionic radii satisfy the structural constraints, volume and planar,
imposed by the simple ideal Perovskite structure. Note that each color (gray, blue, cyan,
 Perovskites: Temperature Dependent Ionic Radii 3
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Figure 1. Solutions, in ionic radii space, to planar and volume constraints of the “simple” “ideal”
cubic Perovskite structure and comparison with Goldschmidt’s tolerance factor, t = 1.00 plane (black
symbols). Five planar constraints, eqn. 1 (gray), eqn. (2) – (blue), eqn. (3) – (cyan), eqn. (4) – (green),
and eqn. (5) – (red), with openings in four out of five planes, all but (gray), occur due to the volume
constraint, eqn. (6). Intersection of two or more constraint planes represents a region of increasing
stability where more than one plane simultaneously defines the crystal lattice parameter.

green, and red) in ionic radii space represent the constraint planes:

a
0 < RA ≤ (1)
2
a √ 
0 < RA + RC ≤ 2 (2)
2
√ 
a 2
0 < RC ≤ (3)
2 2
a
0 < RB + RC ≤ (4)
2
a √ 
0 < RA + RB ≤ 3 (5)
2
 4 V. L. Miller and S. C. Tidrow

respectively. These constraints physically define the lattice parameter of the simple ideal
Perovskite structure. Openings in four of the five structural constraint planes occur due to
limitations imposed on ionic radii through the volume constraint,
4π  3 4π  
Ri = (RA )3 + (RB )3 + 3 (RC )3 < a 3 (6)
3 3
which mathematically indicates that the sum of the volumes of each of the A-site, B-site
and C-site atoms in the structure must be less than the volume of the structure defined by the
lattice parameter. There are other constraints, which have not yet been addressed [6], that can
be used to further slightly reduce possible solutions within ionic radii space that physically
define the formation of simple ideal Perovskite materials. The planar and volume constraint
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model presented by Tidrow [6] that addresses the simple ideal Perovskite structure through a
cubic ionic radii space can be modified to include tetragonal, orthorhombic, rhombohedral,
etc., Perovskite crystal structures and it can also be modified to include general, non-
Perovskite, crystal structures.
In ionic radii space, Fig. 1, the regions of intersection of planes represent greater
lattice stability with the intersection of two planes representing the lattice parameter at
which either of two constraint planes simultaneously defines the lattice parameter of
the simple ideal Perovskite structure. Note that there are three points of highest stabil-
√ √ √ √ √ √ √
ity ( 4 , 2 (1 − 2 ), 4 ), ( 2 , 2 (2 − 2), 21 ( 2 − 1)), and, ( 21 , 21 ( 3 − 1), 21 (2 − 3)) which
2 1 2 2 1 1

represent the points where three planes intersect and where each of the three planes si-
multaneously defines
√
the √lattice
√
parameter of the simple ideal Perovskite material. The
stability point ( 42 , 12 (1 − 22 ), 42 ), straddles the RC plane, eqn. (3), the RA -RC plane, eqn.
√ √
(2), and, the RB -RC plane, eqn. (4). The point ( 12 , 21 (2 − 2), 21 ( 2 − 1)) straddles the RA -
√ √
RC plane, RB -RC plane and the RA plane. The point ( 21 , 12 ( 3 − 1), 21 (2 − 3)) straddles
the RA plane, the RB -RC plane, and the RA -RB plane. Superimposed in ionic radii space,
is Goldschmidt’s tolerance plane [6], t = 1.00 for cubic materials (black symbols), which
cuts through the solutions to the structural constraints of the simple ideal Perovskite struc-
ture near high stability points, i.e. the intersections of two or more planes. As pointed out
by Tidrow [6], the new volume and planar constrained model has some consistency with
Goldschmidt’s formalism, a correlation study, yet, the new model illustratively indicates
why Goldschmidt’s tolerance factor is inconsistent with mounting experimental evidence
that shows cubic materials may have tolerance factors relatively far from t = 1.00 as well
as why non-cubic materials may have tolerance factors very nearly t = 1.00. Hence, the
newly introduced model overcomes numerous inconsistencies of Goldschmidt’s formalism
through providing a more thorough framework, although still incomplete, for understanding
which materials should form the Perovskite cubic structure, which materials should form
the non-cubic Perovskite structure, and, which materials should not form the Perovskite
structure.

Inadequacy of Room Temperature Ionic Radii

The two material series, SrB4+O3 and PbB4+O3 , where B4+ may be Am, Bi [13, 14], C
[15], Ce [16, 17], Cm, Co [18], Cr [19], Fe, Ge, Hf [20], Ir, Mn, Mo [21], Nb, Ni [22], Np,
Os [23], Pa, Pb [24], Pd, Po, Pr [25], Pt, Pu [26], Re, Rh [27, 28], Ru [29, 30], S [31], Se
[32], Si [33], Sn [34], Ta, Tb [35, 36], Tc [37, 38], Te [39, 40], Th, Ti [17, 41], U [42, 43], V,
W, or Zr [44], are mapped into simple ideal Perovskite ionic radii space, Fig. 2, using room
temperature ionic and anionic crystal radii of Shannon [5] as normalized through dividing
 Perovskites: Temperature Dependent Ionic Radii 5

each radii, A-site, B-site and C-site, by the cube root of the “effective” volume of the
material. The bold italicized elements are radioactive materials and must be treated with
special care in material processing and handling. In general, the transformation of data for
mapping into the simple ideal Perovskite ionic radii space is accomplished by first dividing
the volume of the material by the equivalent Z parameter to find the equivalent simple single
unit cell Perovskite volume. Next, the ionic and anionic radii of each constituent comprising
the Perovskite is then divided by the cube root of the cell volume to normalize the ionic or
anionic radii values, which are then mapped into ionic radii space, resulting in one data point
for each material within ionic radii space, Fig. 2, which is an expanded view of Fig. 1 with
Goldschmidt’s tolerance plane t = 1.00 removed. In Fig. 2(a) (left), the majority of material
data points lie on the surface of the RB -RC plane which is related to the B-site and C-site
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atom interaction and distortion, rotation, buckling, etc., associated with the octahedral cage
as formed by the three C-site atoms about the B-site atom in the Perovskite structure. The
symbols in red are for non-cubic SrB4+O3 materials at room temperature and the symbols
in red outlined in black are for SrB4+O3 materials that are cubic at room temperature or
are known to become cubic at elevated temperature. The symbols in gray are for non-cubic
PbB4+O3 materials at room temperature while the symbols in gray outlined in black are
for PbB4+O3 materials that are cubic at room temperature or are known to become cubic at
elevated temperature. In Fig. 2(b) (right), many of the data points, especially those of cubic
materials in the SrB4+O3 and BaB4+O3 (not shown here for brevity) series, lie outside the
surface, RA -RC plane. As a result, one can conclude that the revised crystal radii of Shannon
consistently overestimate the “effective” ionic radii of atoms in the Perovskite structure
and thus result in an overestimate of the lattice parameter for these materials. Therefore,
the ionic radii for Perovskite materials need to be re-evaluated at room temperature and
extended using the planar and volume constrained ionic radii model to include temperature

Figure 2. Material data points for LaAlO3 (black) and two series of materials SrB4+O3 (red) and
PbB4+O3 (gray) in simple ideal Perovskite ionic radii space. Materials that are cubic at room temper-
ature or become cubic at elevated temperature are outlined with black circles. The data points have
been calculated using revised room temperature ionic radii of Shannon[5] as mapped into ionic radii
space through normalization (dividing the ionic radii by the cube root of the “effective” simple ideal
Perovskite volume for the material as determined using data from the literature [13–44]).
 6 V. L. Miller and S. C. Tidrow

Single Atom Quantum Well

1.2

1.0

0.8

0.6
V(r)

0.4
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0.2 R
0.0

R
-1.0 -0.5 0.0 0.5 1.0

Normalized Radial Distance

Figure 3. Schematic view, not to scale, of the quantum mechanical potential well of an atom within a
material. The “effective” radius of an atom increases, to first order approximation, relatively linearly
with temperature over an extened temperature range and results equivalently in the observed classical
thermal expansion coefficient for an isotropic material. (Color figure available online.)

dependent ionic radii which can improve the modeling accuracy to a priori more precisely
predict the lattice parameter of Perovskite materials at all allowable temperatures.

Thermal Expansion
Thermal expansion of an isotropic medium, whether the system is linear, area or volumetric,
is classically described in introductory physics courses through the use of an appropriate
linear, area, or volumetric expansion coefficient, α L , α A , or α V , respectively. For an isotropic
material the expansion coefficients are interrelated with α A = 2α L and α V = 3α L . Such
a classical mechanics construct, isotropic material, can be extended to the atomic scale
and applied to model the atom as an “isotropic” coordination dependent “hard” sphere.
Further, this classical concept of thermal expansion has an analogous quantum mechanical
construct. For instance, the potential well of an isolated quantum mechanical system may be
considered to remain constant for a particular situation like that for an isolated atom, Fig. 3,
or that of a linear, area or volumetric array of atoms. In such constructed systems, thermal
energy, kT, is typically small compared with barrier potential heights. Thus, thermal energy
can be conceptualized to slightly change or perturb the energy level of the electron(s) within
the well while leaving the shape of the well alone. The thermal energy transferred to or from
the atom can be viewed to first order approximation as an addition or reduction of kinetic
energy of the electron(s) that results in a higher or lower potential energy of the electron(s)
level in the well. Such differences in thermal energy change the “effective” average radius
of the atom through the oscillatory motion of the energetic electron(s) in the potential well.
For small thermal changes or small perturbations of the energy level of the electron(s) in the
potential well, the “effective” ionic radii of the atom changes to first order approximation
as a linear function of temperature. Hence, the classical and quantum approach are to first
 Perovskites: Temperature Dependent Ionic Radii 7

order equivalent and the relation:

ri (T ) = rio (1 + αi T ) (7)

can be used to express the “effective” ionic radius, ri (T), at temperature T where rio is the
low temperature (0 K) ion or anion radius, and α i is the linear expansion coefficient for each
particular ion or anion, respectively. Note that at extreme temperatures: (1) below about
50 K; (2) at high temperatures, near the melting temperature of the material; or (3) in other
special situations; higher order quantum mechanical terms may become significant and the
above model may be modified to fit the conditions through including higher order terms in
the approximation.
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Data and Fitting

Temperature dependent data, of 25 simple ideal Perovskite materials, AgNbO3 [45],
AgTaO3 [45], KNbO3 [46], KTaO3 [47], NaNbO3 [46, 48], NaTaO3 [48, 49], BaCeO3
[50, 51], BaTiO3 [52], BaUO3 [53], BaZrO3 [53], CaTiO3 [54], PbHfO3 [55], PbTiO3
[56], PbZrO3 [57], SrHfO3 [58], SrMoO3 [59],SrRuO3 [60, 61], SrTcO3 [62], SrTiO3 [63],
SrZrO3 [63], CeAlO3 [64], LaAlO3 [65], KMgF3 [66], KMnF3 [67], and, NaMgF3 [66],
have been utilized in a non-linear regression fitting program, NLREG Version 6.5 (Ad-
vanced) by Phillip H. Sherrod, to determine the “effective” temperature dependent ionic
radii for 12-fold coordinated ions Ag1+, K1+, Na1+, Ba2+, Ca2+, Pb2+, Sr2+, Ce3+, and,
La3+, 6-fold coordinated ions Mg2+, Mn2+, Al3+, Bi3+, Ce4+, Hf 4+, Mo4+, Ru4+, Tc4+, Ti4+,
U4+, Zr4+, Nb5+, and, Ta5+, and, 6-fold coordinated anions O2−, and F1−, using the planar
constrained and volume restricted simple ideal Perovskite model, Fig. 1. Our program is cur-
rently constructed to simultaneously address 27 different coordination dependent elemental
atoms in the 12-fold coordinated A-site, 173 different coordination dependent elemental
atoms in the 6-fold coordinated B-site, 9 different coordination dependent elemental atoms
in the 6-fold coordinated C-site. Additionally, our model accommodates for formation of
Perovskite cubic solid solutions through A-site to A-site, B-site to B-site, and C-site to
C-site mixing of elemental atoms. Thus far, we have investigated and confirmed that the
anionic and ionic radii parameters obtained from the simple ideal Perovskite materials
reproduce, typically to within less than 1% error, the experimental, temperature dependent,
lattice parameters of over 25 simple ideal Perovskites and about 75 cubic Pervoskite solid
solutions found in the literature involving these anions and ions.

Results: Determination of Coordination and Temperature Dependent

Ionic Radii
Currently, the accepted room temperature value for the anionic radius of oxygen, O2−, is in
the range 1.26 to 1.40 Å [5]. Here, through investigating numerous simple ideal Perovskite
materials, an upper limit on the size of the oxygen anionic radius at room temperature is
determined to be less than 1.34 Å. The upper limit for each of the possible C-site anions that
can form the Perovskite structure can be determined through using materials that have the
smallest known temperature dependent simple ideal Perovskite lattice parameter for each of
the possible C-site atoms (if they exist), respectively. For simple ideal Perovskites contain-
ing oxygen on the C-site, LaAlO3 , a special case of the simple ideal Perovskite, presently
has the smallest known lattice parameter. LaAlO3 is rhombohedral, at room temperature,
 8 V. L. Miller and S. C. Tidrow

and transforms into and remains in the simple ideal Perovskite state at temperatures above
about 820 K [65], and has a melting point of 2453 K [6]. The lattice parameter of LaAlO3
as a function of temperature has been reported by Howard and Kennedy [65]. Through per-
forming a non-linear regression fit to the temperature dependent lattice parameter of LaAlO3
using eqn. (7) within eqn. (3) to account for thermal expansion and eqn. (6) to account for
permissible fill factors, the upper limit to the oxygen anion is determined to be 1.3342 Å (at
0 K) with linear expansion coefficient α O = 1.18 × 10−5 K−1. The model, fitting routine,
which currently searches for positive values for the coefficient for linear expansion, can
easily be adapted to search for negative coefficients of expansion if physical constraints on
the system so warrant. Since the calculated room temperature value, as determined using
the two fitting parameters for oxygen, lies between the lower and upper accepted value for
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the room temperature radii of oxygen [5], we assume in this paper that this upper limit to
the size of oxygen is the current “best” value for the anionic radius of oxygen in the simple
ideal Perovskite structure. Now that the anionic radius for oxygen has been set, non-linear
regression fitting can be performed on other temperature dependent data to determine each
of the other ions that form the simple ideal Perovskite oxide structures. Due to the size
of anionic oxygen within simple ideal Perovskites, planar constraints, eqns. (1) and (5) in
conjunction with the volume constraint, eqn. (6), can be difficult and even impossible to
satisfy; therefore, ionic radii search space is primarily reduced to the planar constraints,
eqns. (2) and (4), in conjunction with the volume constraint, eqn. (6). Since 6-fold B-site
atoms are consistently smaller than 12-fold A-site atoms, materials that have smaller lattice
parameters within a series of simple ideal Perovskites are fit using eqn. (7) within the planar
constraint, eqn. (4), while larger lattice parameter materials in the series are fit using eqn.
(7) within the planar constraint, eqn. (2), in conjunction with the volume constraint, eqn.
(6). Materials that satisfy a particular planar constraint model, through reasonably “good”
fit, are kept as data within that modeled constraint. Materials that can’t be readily fit to
the particular constraint are removed as data for that constraint. Some materials satisfy,
to reasonably “good” fit, either planar constraint condition and continue to be utilized as
data within both constraint models. The fitting routine does not presently allow automatic
binning of the data of a particular material into one or multiple planar constraint models.
Such binning is accomplished through the operator who checks for consistency of the fit
to the data while trying to maximize the stability condition for the totality of the materials.
We have attempted to find solutions that increase the integrity of the structure by favoring
solutions that are close to the higher stability regions, Fig. 1, intersections of two or more
structural planar constraints in simple ideal Perovskite ionic radii space. Note, the solutions
found and presented here are not a set of unique expressions since mathematically the
system is over determined; however, we have attempted to find and utilize solutions that
are consistent to the physical constraints as well as consistent with literary values for ionic
radii at room temperature. As more temperature dependent lattice parameters from simple
ideal Perovskite materials are added to the model, the results presented here may become
obsolete; however, at present they are able to reasonably reproduce temperature dependent
lattice parameters of 25 simple ideal Perovskites and about 75 solid solution cubic Per-
ovskite materials using linear thermal expansion coefficient and coordination dependent
ionic radii for each of 25 ions. The materials discussed here, BaTiO3 , CaTiO3 , PbTiO3 and
SrTiO3 exhibit simple ideal Perovskite lattice parameters at temperatures above 393 K,
1173 K, 763 K and at all measured temperatures, respectively, and likely remain cubic up
to their melting temperatures of 1883 K, 2248 K, not reported, and 2353K [6], respec-
tively. The values for the 19 ionic radii not reported here will be reported in a subsequent
paper.
 Perovskites: Temperature Dependent Ionic Radii 9

CaTiO3 , which is non-cubic at room temperature, has, at elevated temperature, the

smallest lattice parameter or volume of any of the simple ideal Perovskite materials in this
A2+TiO3 series. Therefore, CaTiO3 places a limit on the maximum size of the combined
Ti and O ionic radii through the Ti O direction since oxygen is not large enough to satisfy
eqn. (3). Again, if oxygen to oxygen contact occurs in the simple ideal Perovskite structure,
it occurs in LaAlO3 which has a smaller lattice parameter than CaTiO3 . Since we have
already set the anionic radii parameters of oxygen in the simple ideal Perovskite oxide
structure, then Ti has a size about 0.5763 Å with expansion coefficient 1.886 × 10−5 K−1
as obtained through non-linear regression fitting of the data. Performing fits to the material
data, it is determined that Ba, Ca, Pb and Sr possess ionic radii that are 1.4863 Å, 1.3677
Å, 1.4440 Å, and, 1.4168 Å at 0 K, respectively, with linear expansion coefficients of 1.47
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× 10−5 K−1, 1.12 × 10−5 K−1, 1.22 × 10−5 K−1, and, 1.02 × 10−5 K−1, respectively. The
parameters for the ionic radii in 12-fold coordination, Ba2+, Ca2+, Pb2+, Sr2+ and La3+,
and 6-fold coordination, Ti4+ and O2−, are summarized in Table 1.
As shown in Fig. 4, the data generated from the parameters reported in Table 1
reproduce the lattice parameter conditions for LaAlO3 , and the A2+TiO3 materials, where
A is Ba, Ca, Pb and Sr. The non-linear regression fitting routine, NLREG a commercially
available software package, has been utilized to fit 177 temperature dependent data points
from 25 simple ideal Perovskite materials, AgNbO3 [45], AgTaO3 [45], KNbO3 [46],
KTaO3 [47], NaNbO3 [46, 48], NaTaO3 [48, 49], BaCeO3 [50, 51], BaTiO3 [52], BaUO3
[53], BaZrO3 [53], CaTiO3 [54], PbHfO3 [55], PbTiO3 [56], PbZrO3 [57], SrHfO3 [58],
SrMoO3 [59],SrRuO3 [60, 61], SrTcO3 [62], SrTiO3 [63], SrZrO3 [63], CeAlO3 [64],
LaAlO3 [65], KMgF3 [66], KMnF3 [67], and, NaMgF3 [66] to determine the temperature
dependent ionic radii for 12-fold coordinated Ag1+, K1+, Na1+, Ba2+, Ca2+, Pb2+, Sr2+,
Ce3+, and, La3+, 6-fold coordinated Mg2+, Mn2+, Al3+, Bi3+, Ce4+, Hf 4+, Mo4+, Ru4+,
Tc4+, Ti4+, U4+, Zr4+, Nb5+, and, Ta5+, and 6-fold coordinated O2− and F1−. Final sum of
squared deviations range from 1.33 × 10−3 to 2.92 × 10−1. Final sum of deviations range
from 1.0 × 10−6 to 1.32 × 10−3. Standard error of estimates range from 2.1 × 10−2 to 1.06
× 10−1. Average deviations range from 6.9 × 10−3 to 2.7 × 10−2. Maximum deviation for
any observation range from 1.2 × 10−2 to 1.3 × 10−1. Proportion of variance explained

Table 1
Determined Perovskite ionic and anionic radii values

Shannon Shannon
Linear Crystal Ionic Perovskite
Site Expansion Radius Radius Radii Here
Ion or and roi (Å) Coefficient (Å) (@ (Å) (@ (Å) (@
Anion C.N. @0K α I (10−5)/K 293K) 293K) 293K)
O2− C-6 1.3342 1.18 1.26 1.40 1.3389
Ba2+ A-12 1.4863 1.47 1.75 1.61 1.4927
Ca2+ A-12 1.3677 1.12 1.48 1.34 1.3722
Pb2+ A-12 1.4440 1.22 1.63 1.49 1.4492
Sr2+ A-12 1.4168 1.025 1.58 1.44 1.4211
Ti4+ B-6 0.5763 1.09 0.745 0.605 0.5763
La3+ A-12 1.3342 1.18 1.50 1.36 1.3389
Al3+ B-6 0.5540 1.12 0.675 0.535 0.5459
 10 V. L. Miller and S. C. Tidrow

BaTiO3, CaTiO3, PbTiO3, SrTiO3 and LaAlO3

4.2

4.1

Lattice Parameter (Å)

4.0

3.9
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3.8
400 600 800 1000 1200 1400 1600 1800

Temperature (K)

Figure 4. Data for LaAlO3 (pink symbols) [65], CaTiO3 (red symbols) [54], SrTiO3 (black symbols)
[63], PbTiO3 (blue symbols) [56], and BaTiO3 (green symbols) [52] having the simple ideal Perovskite
structure above 820 K [65], 1173 K [54], at all measured temperatures, 763 K [6], and, 393 K [6],
respectively, are fit using the parameters from Table 1, and yield the appropriately color coded dotted
lines.

(R2) range from 0.9992 to 1. Adjusted coefficient of multiple determination (Ra2) range
from 0.9993 to 0.9999. Durbin-Watson test for autocorrelation range from 1.246 to 2.137.
F values from 232 to 7294 and Prob(F) range from 1 × 10−5 to 4.1 × 10−4.
Utilizing the same fitting routine as used to determine the ionic radii parameters re-
ported in Table 1, we have investigated 20 other simple ideal Perovskite materials containing
another 19 coordination dependent ions. While the ionic radii parameters for those 19 co-
ordination dependent ions will be reported elsewhere, we can state that the radii parameters
for these 19 ions reproduce temperature dependent lattice parameters of 19 other simple
ideal Perovskite materials, which visually provide fits to those materials which are for the
most part similar to those of Fig. 4 and with all typically producing less than 1% error in
fit to lattice parameters using the simple ideal Perovskite modeled materials. In addition,
the totality of the 25 ions also reasonably well reproduce, typically less than 1% error,
the temperature dependent lattice parameters of over 50 ideal Perovskite solid solutions
involving combinations of the 25 ions investigated thus far. Using some of these yet to be
reported parameters for the 19 ionic radii, we re-evaluate and plot within ionic radii space,
Fig. 5, several materials of the series A2+(B4+)O3 , where A is Ba, Ca, Pb, Sr and B is Ce,
Hf, Mo, Ru, Tc, Ti, U, Zr using the same normalization procedures as were performed on
the data of Shannon [5], Fig. 2.
In Table 2, several parameters are reported in column 1 for materials, BaTiO3 , CaTiO3 ,
PbTiO3 , SrTiO3 , and LaAlO3 , investigated in this paper, plus BaUO3 . The tolerance fac-
tor for the particular material, using Shannon data [5] within Goldschmidt’s formalism,
is reported in column 2. The reported lattice parameter for each material, at the cubic
phase transition or at room temperature, whichever temperature is higher, is reported in
column 3. The lattice parameter as modeled using revised ionic radii of Shannon [5] at
room temperature within Goldschmidt’s formalism [3] is reported in column 4. The lattice
 Perovskites: Temperature Dependent Ionic Radii 11
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Figure 5. Several of the materials in the series Sr(B4+)O3 and Pb(B4+)O3 of Fig. 2 are plotted
using ionic radii values determined using the simple ideal Perovskite model presented in this paper.
The ionic radii determined using this simple ideal Perovskite model provide greater consistency for
understanding the formation of Perovskites materials, whether they will be cubic or non-cubic, and
provide improved accuracy and precision for determination of room temperature lattice parameters
of simple ideal Perovskites and determination of their lattice parameters as a function of temperature
as compared with Goldschmidt’s formalism using data of Shannon [5].

parameter obtained using coordination and temperature dependent data reported in this
paper as obtained using the construct of Tidrow [6], is reported in column 4, obtained
from room temperature data or data at the cubic phase transition, whichever temperature
is higher. The lattice parameter, column 5, is the largest lattice parameter that satisfies the

Table 2
Material parameters comparing models

Tolerance Tolerance
Factor Goldschmidt Actual Tidrow RA +RC RC RB +RC Factor
Shannon Lattice Lattice Lattice Plane Plane Plane Tidrow
Material Data (Å) (Å) (Å) (Å) (Å) (Å) Data
BaTiO3 1.062 4.133 4.0106 4.0096 4.0096 3.7912 3.8382 1.045
(393 K)
CaTiO3 0.966 3.942 3.8837 3.8837 3.8837 3.8372 3.8837 1.000
(1423 K)
PbTiO3 1.019 4.049 3.9663 3.9644 3.9644 3.8072 3.8541 1.029
(750 K)
SrTiO3 1.002 4.013 3.9040 3.9034 3.9034 3.7872 3.8343 1.018
(293 K)
LaAlO3 1.009 3.887 3.8106 3.8104 3.8104 3.8104 3.7932 1.005
(821 K)
BaUO3 0.929 4.418 4.1920 4.1917 4.0044 3.7869 4.1917 0.955
(293 K)
 12 V. L. Miller and S. C. Tidrow

construct of Tidrow [6], eqn. (1), eqn. (2) listed in column 6, eqn. (3) listed in column 7,
eqn. (4) listed in column 8, and, eqn. (5) while satisfying the volume constraint eqn. (6).
Goldschmidt’s tolerance factor is reported in column 9 using coordination and temperature
dependent data reported in this paper as obtained using the construct of Tidrow [6]. From
Table 2, the tolerance factor has significant variance from 1.00; yet, each material is either
cubic at room temperature or becomes cubic at elevated temperatures. Since the tolerance
factor for a particular material depends on the ratio of atoms describing two planar con-
straints, it changes rather slowly, on the order of the ratio of the thermal coefficients of the
atoms constructing the planar conditions, eqns. (2) and (4), which presently are the primary
planes involved in the construction of the simple ideal Perovskite structure. Therefore, as
a function of temperature, the material data point in ionic radii space does not typically
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move far from its original spot. Hence, one may conclude that the tolerance factor cannot
adequately account for the formation of materials like BaTiO3 and BaUO3 of Table 2.
Thus, Goldschmidt’s formalism, while having inspired the search for, and discovery and
development of a wide range of Perovskite materials, does not provide a physically sound
model for the continued search, discovery and development of new Perovskite materials.
It appears that the construct provided in this paper, Fig. 1, as highlighted in Fig. 5, may
provide a direction for improving our ability to understand whether or not a material will
form with the ideal Perovskite structure. In Fig. 5, material data points lying near the surface
of one of the planar constraints tend to be cubic with the two Sr based materials, SrCeO3
and SrUO3 , being exceptions. SrCeO3 and SrUO3, which lie near the surface of the planar
constraint, eqn. (4), the RB -RC plane, do not meet the volume constraint, eqn. (6), which
results in the hole in the planar constraint, eqn. (4). Hence, the ionic ratios for SrCeO3 and
SrUO3 do not support formation of the simple ideal Perovskite structure. Therefore, volume
constraints may be a cause of such non-cubic Perovskite structures. Further, as presented
by Tidrow [6], polarization induced structural phase transitions, a direct consequence of
the Clausius-Mossotti relationship [68–70] through the “dielectric catastrophe”, may be a
primary factor for temperature induced structural phase transitions in Perovskite materials.

Summary
A new model that was recently introduced, based on physical constraints [6] rather than
semi-empirical relations [3], has been expounded upon in this paper and utilized to de-
termine the “effective” temperature dependent ionic radii of 12-fold coordinated, Ba2+,
Ca2+, Pb2+, Sr2+ and La3+, and 6-fold coordinated, Ti4+ and O2−, within the simple ideal
Perovskite structure. The determined “effective” ionic radii accurately reproduce the lat-
tice parameters of simple ideal Perovskite materials to high precision. Common features
between this new model and Goldschmidt’s tolerance planes have been discussed and dif-
ferences in the two models have been shown. The utilized model has improved accuracy
over that of Goldschmidt’s formalism for predicting whether or not a formed Perovskite
material will be cubic or non-cubic. The new model indicates that there are additional
regions in ionic radii space to search, outside Goldschmidt’s tolerance range, which may
yield new ideal Perovskite materials. Further, the new model provides more precise lattice
parameter determination of Perovskite materials at room temperature than can be attained
using revised crystal radii of Shannon [5] within Goldschmidt’s formalism [3]. This new
model, as explicitly demonstrated within this paper, can be used to precisely model the
lattice parameter of simple ideal and ideal Perovskite materials over extended temperature
ranges. Presently, the eight “effective” ionic radii reported here and the additional nineteen
 Perovskites: Temperature Dependent Ionic Radii 13

that will be reported elsewhere currently provide highly accurate, precision lattice parame-
ters to 25 simple ideal Perovskites and over 50 additional solid solution ideal Perovskites.
This new developing model can be used as a stand-alone construct to significantly reduce
the ionic radii search space and help reduce the time for discovery and development of new
Perovskite materials.

Future Directions
We believe continued development of the planar and volume constrained simple ideal
Perovskite model with extension to non-ideal Perovskites and even non-Perovskites through
physical constraints and mapping of various crystal structures into ionic radii space will
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ultimately lead to improved models that reduce the time and cost of developing affordable
materials that have properties that outperform materials in current technologies as well as
provide novel properties that allow for the development of new technologies. High precision
lattice parameter determination is important for increasing the accuracy in determining the
energy or polarization per unit volume in the lattice which can be used to determine the
dielectric constant of materials as a function of temperature. Such precise temperature
dependent lattice parameters can also be used to determine the temperature at which
polarization induced structural phase transitions occur as addressed using the Clausius-
Mossotti [68–70] relation for dielectric constant and through the “dielectric catastrophe”
[69, 70] for polarization induced structural phase transitions using the unit cell volume
and the total polarizability of atoms within the unit cell. The current room temperature
polarizability of ions as reported by Shannon [69] provides a reasonable starting point
for estimating the temperature of structural phase transitions using temperature dependent
volume which can now be more precisely determined using “effective” ionic radii developed
and reported in this paper. Further improvements in the prediction of temperatures for
structural phase transitions will occur through refinement of ionic polarizability of atoms
as a function of temperature which can be performed through using dielectric constants
of materials as a function of temperature in conjunction with lattice volume of materials
as a function of temperature within a non-linear regression fitting program that uses the
Clausius-Mossotti formula for parametric fitting.

Acknowledgments
This material is based upon work supported by, or in part by, the U.S. Army Research
Laboratory and the U.S. Army Research Office under contract/grant number W911NF-08-
1-0353. The author S.C. Tidrow would like to thank Dr. Art Tauber and Professor Amar
Bhalla for many constructive discussions pertaining to development of new Perovskite
oxide materials.

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