Phys Chem Minerals
DOI 10.1007/s00269-013-0611-7
ORIGINAL PAPER
The Loewenstein rule: the increase in electron kinetic energy
as the reason for instability of Al–O–Al linkage
in aluminosilicate zeolites
Alexander V. Larin
Received: 7 March 2013 / Accepted: 24 June 2013
 Springer-Verlag Berlin Heidelberg 2013
Abstract Problem of Al–O–Al linkage in aluminosilicate
materials or Al-avoidance is discussed for two zeolite
structures (phillipsite and brewsterite) exchanged with
Mg2? cations. All models are fully optimized at periodic
Hartree–Fock and hybrid density functional theory levels
(the CRYSTAL code). Their properties are then calculated
at the periodic level with the same basis sets. The reasons
for the instability of the zeolite structures including the
Al–O–Al moieties are interpreted on the basis of cell
energy decomposition. This destabilization comes from an
increase in kinetic energy if the Al–O(Mg)–Al moieties are
present in zeolites. This effect is discussed in parallel with
already known variational evidences in favor of dominat-
ing role of kinetic energy for stability of molecular
systems.
Keywords Aluminosilicates  Loewenstein rule 
Al-avoidance  Zeolite  Periodic density functional theory 
Periodic Hartree–Fock  Electron kinetic energy 
Aluminosilicate glass
Electronic supplementary material The online version of this
article (doi:10.1007/s00269-013-0611-7) contains supplementary
material, which is available to authorized users.
A. V. Larin (&)
Department of Chemistry, Moscow State University,
Leninskie Gory, 119991 Moscow, Russia
e-mail: nasgo@yandex.ru
A. V. Larin
OOO Plasmonika, Ural Building, 100, Novaya street, Skolkovo
startup Village, Odintsovsky district, 143025 Moscow, Russia
Introduction
The Loewenstein rule states avoidance of Al–O–Al moie-
ties in aluminosilicate crystalline materials or Al-avoidance
(Loewenstein 1954) serving till now as a landmark for fine
inorganic synthesis (Gonzalez-Gallardo et al. 2011).
Another relevant conclusion about the zeolite composition
is formulated as Dempsey rule that confirms a minimum
number of the –Al–O–Si–O–Al– fragments in a zeolite
(Ramdas et al. 1981; Engelhardt et al. 1981; Melchior et al.
1982). A probability of the Al–O–Al appearance in the
aluminosilicates could be evaluated on the basis of exper-
imental 17O determination with MAS NMR technique. It
was tentatively estimated less than 2.0 % (Pingel et al.
1998) in low-silica A zeolites where the populations of
other Si–O–Si and Si–O–Al species were estimated (Zhao
et al. 2001). The absence of the Al–O–Al linkage in other
low silica X (Pingel et al. 1998; Zhao et al. 2001), analcime
(Zhao et al. 2001), as well as in high-silica ZSM-5 (Pingel
et al. 1998) zeolites was also confirmed by MAS NMR in
opposite to low-silica glasses (Lee et al. 2000). Appearance
of Al–O–Al moieties for the latter was interpreted as a
consequence of meta-stable disorder in the course of high-
temperature glass formation (Zhao et al. 2001). Other
arguments in favor of chemical kinetic factors were for-
mulated by (Pelmenschikov et al. 1992). The authors
evaluated that the possibility of decomposition is higher for
the structure with two closest Al atoms. The values were
obtained on the basis of the HF/STO-3G energy estima-
tions for framework ‘‘elements’’ such as (HO)3Si–O–
Al(H2O)(OH)3 used to simulate reactions in zeolites. The
authors emphasized that ‘‘chemical’’ attraction is the rea-
son for the easiness of Al extraction from a framework and
not the electrostatic repulsion between two Al atoms in
framework as proposed earlier (Dempsey 1974; Mikovsky
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 Phys Chem Minerals

and Marshall 1976; Mikovsky and Marshall 1979). Alter- Table 1 Lattice parameters a, b, c, b (Å, degrees) for MgPHI and
natively, Catlow et al. (Catlow et al. 1996) approved the MgBRE zeolites both possessing P21/m symmetry group and opti-
mized at the PDFT/B3LYP level with 85-11G*(Mg, Al)/88-31G*(Si)/
domination of thermodynamic factors also at the level of
6-31G*(O) level
isolated cluster calculations. Any microscopic reason
behind this energy gain for aluminosilicate zeolites obey- Type a b c b
ing to the Loewenstein rule (Loewenstein types or LT) was Loewenstein Mg-models
not discussed to our best knowledge. Resuming, one should PHI32 9.9413 12.1910 8.1126 128.91
notice that relative stabilities of the LT group have not PHI21 10.3958 12.9828 8.6942 128.01
been yet compared using ab initio or DFT computation PHI15 10.3965 12.9873 8.6868 127.93
with periodic boundary conditions to that of non-Loe- PHI11 10.3953 12.9812 8.6347 127.40
wenstein (NL) zeolite types containing Al–O–Al moieties. Non-Loewenstein Mg-models
One of the problems for theoretical explanation of the
PHI10 10.1619 13.8497 8.8163 128.02
Al-avoidance in zeolites is related to the absence of any
PHI26 10.1903 13.7437 8.8212 128.52
zeolite for which Al-avoidance is violated and experi-
PHI12 10.6543 13.0677 8.0525 126.87
mentally approved. Though the Al–O–Al linkage occurs in
Theorya 9.861 14.093 8.667 124.68
aluminates and aluminosilicate glasses, it is difficult to
Experimentb 9.865 14.300 8.668 124.20
propose an appropriate scheme of two similar computa-
9.879 14.139 8.693 124.81
tions, one, for example, with an aluminate and another with
Loewenstein Mg-models
a zeolite, which could demonstrate the disfavor situation
BRE6 6.8172 15.9185 7.7110 94.98
for the Al–O–Al in the zeolite.
BRE4 6.9231 15.7170 7.35823 93.41
In this work, we develop such scheme to compare
BRE5 6.6651 16.0025 7.56017 94.71
properly the stabilities of hypothetic NL zeolites with the
Non-Loewenstein Mg-models
Al–O–Al groups with those of real zeolites. For this, it is
suggested to consider at quantum chemical level the most BRE49 6.8800 17.6344 7.7662 95.40
favored electrostatic situation for stabilization of the BRE51 6.9126 18.1914 7.6348 96.83
Al–O–Al linkage by divalent compensating cation. The BRE50 6.8481 17.0317 7.5781 94.04
advantage of divalent cation as compared to monovalent Experimentc 6.793 17.573 7.759 94.54
one is connected with the absence of Coulomb repulsion a
All-siliceous model optimized with empirical force field in (Dovesi
between two monovalent cations that both should com- et al. 2006)
b
pensate the charge of the Al–O–Al moiety and should be Si/Al = 2.019 and 3.0 in the first K2Ca1.648(H2O)12Si10.7Al5.3O32
closely located one to another. Indeed, the higher fraction and second Ba2Ca0.6(H2O)12Si12Al4O32 cases, respectively, from
(Rinaldi et al. 1974)
of the Al–O–Al moieties in low silicate Ca-glasses rather c
Si/Al = 3.0 for Ba0.52Sr1.48(H2O)10Si12Al4OÅ from (Schlenker
than in Na-glasses (Cormier et al. 2003) can be interpreted et al. 1977)
as stabilizing effect of divalent cation. One of the expla-
nations of the preference of divalent cation is related to
decrease in the enthalpy of Si–Al ordering (Lee et al. exchange) with the 85-11G*(Mg, Al)/88-31G*(Si)/
2000). 6-31G*(O) basis set involving cell parameters (Table 1) with
periodic boundary conditions. For all cases, the thresholds
Computational details for the electronic integral calculations were fixed to 10-5
for the overlap Coulomb, penetration Coulomb, and over-
Two frameworks of phillipsite and brewsterite zeolites lap exchange and to 10-7 and 10-10 for the pseudo-overlap
(both possessing P21/m spatial symmetry group) have been exchange for different summation indexes. SCF FMIXING
chosen. Natural K/Ca- and Ca/Ba-phillipsites (Rinaldi et al. convergence parameter (30 %) was applied. B3LYP was
1974) and Sr/Ba-brewsterites (Schlenker et al. 1977) occur shown to be accurate for evaluation of relative stabilities of
with Si/Al modulus of 2.019 and 3.0, respectively all-siliceous zeolites (Catti et al. 2000). The B3LYP
(Table 1). The models which include Al–O–Al moieties or functional provides very similar electron density distribu-
non-Loewenstein (NL) zeolite types have been obtained by tion represented via atomic multipoles for aluminophos-
replacing heavier cations (K, Ca, Sr, Ba) with the smaller phates relative to PW91 functional, while minor
Mg ones, Si with Al atoms at T(2) or T(4) sites in PHI and differences have been observed versus the atomic multi-
T(3) site in BRE, respectively. poles calculated with PBE (Larin et al. 2005). Direct
Geometry optimization war performed using CRYS- scaling of wavefunction was performed to optimize the
TAL06 (Dovesi et al. 2006) code and hybrid density basis set in the similar way with a common a parameter for
functional theory (DFT)/B3LYP (30 % of Hartree–Fock both LT and NL zeolites. Relative energy difference

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Phys Chem Minerals
between LT and NL models has been compared upon the
scaling. Vibrational frequencies were calculated using the
finite difference method as implemented in the CRYS-
TAL06 code. Small displacements (0.00567 Å) of all
atoms were used to estimate the numerical Hessian matrix.
Analogous optimizations of the same BRE and PHI
models at the periodic Hartree–Fock (PHF) level have been
performed applying minimal STO-3G basis set and keeping
the tolerance criterions. The stabilities are then discussed in
the same terms of the ‘‘structure–energy’’ components as
above. Due to totally coherent results at this theory level,
we have presented them in Supplementary Materials.
Results
The geometry of the optimized LT and NL models
and virial ratio
The cell parameters of the optimized LT and NL (Fig. 1)
models are shown in Table 1. This moderate difference in
the cell sizes of the Mg-forms seems to be predicted
Fig. 1 Two non-Loewenstein
(NL) MgPHI10 (a) and
MgBRE51 (b) type zeolites.
The color code is as follows:
O in red, Si in yellow, Al in
violet, Mg in green
regarding that hydrated zeolites with heavier cations (K,
Ca, Sr, Ba) were applied for X-ray experiments (Rinaldi
et al. 1974; Schlenker et al. 1977). The agreement with
experimental cell parameters is better for BRE framework.
Surprisingly, the most accurate optimization of experi-
mental PHI cell sizes was earlier reached with Catlow force
field for all-siliceous PHI model without any cations (Larin
et al. 2008). The geometry of the Mg–OAl2 groups and of
the others is given in Tables 2, 3. The Mg–O bond lengths
(Table 2) are in the conventional range obtained with
cluster calculations (Sykes and Kubicki 1996). The Mg
cation coordination is described via all the nearest O types
in the right column of Table 2. First, in the right column of
Table 2, there are n Mg–O distances for n-coordinated Mg.
Then, there is a symbol containing two parts, i.e., the
coordination number n of the Mg cation and n symbols of
the nearest i-oxygen atoms in the increasing |Mg–Oi| order.
The O symbols are partitioned into three types denoted by
plus, minus, or star (Fig. 2a–c), which relate to the Mg–
OSiAl, Mg–OSi2, or Mg–OAl2 species, respectively. In
order to facilitate the notations in Table 2, the key com-
binations used, i.e., Al–O–Si as ‘‘?,’’ Si–O–Si as ‘‘-,’’
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 Phys Chem Minerals

Table 2 The MgPHI and MgBRE models, positions of the Si atom 85-11G*(Mg, Al)/88-31G*(Si)/6-31G*(O) (shift by DU1 = 7253 a.u.),
replaced by Al in the initial X-ray diffraction models (Rinaldi et al. Upot/Ukin ratio, average Mg–O distance Rav (Å), Mg–O distances, and
1974; Schlenker et al. 1977), framework density (FD, g 9 cm-3), coordination type (Å)
energies U (a.u.) optimized at the PDFT/B3LYP level with
Type Al position FD |U ? DU1| -Upot/Ukin Rav Mg–O distances and coordination typea

Loewenstein (LT) models

PHI32 Al(1) 2.178 0.554083 2.003716 2.097 2 9 2.044, 2.111, 2 9 2.144, 5??-??
PHI21 Al(3) 1.802 0.561645 2.003651 2.048 2 9 2.039, 2 9 2.057, 4????
PHI15 Al(3) 1.801 0.561429 2.003651 2.048 2 9 2.039, 2 9 2.058, 4????
PHI11 Al(3) 1.800 0.565034 2.003637 2.031 2 9 1.979, 2 9 2.082, 4????
Non-Loewenstein (NL) models
PHI10 Al(4) 1.705 0.516355 2.003630 1.922 1.913, 2 9 1.927, 3*??
PHI26 Al(4) 1.724 0.516773 2.003632 1.929 1.915, 2 9 1.936, 3*??
PHI12b Al(2) 1.858 0.365101 2.003666 2.051 2 9 2.042, 2 9 2.061, 4----
Loewenstein (LT) models
BRE6 Al(1) 2.025 0.580203 2.003650 1.999 2 9 2.013, 2 9 2.038, 4????
BRE5 Al(1) 2.073 0.521973 2.003686 2.083 2 9 2.063, 2 9 2.102, 4????
BRE4 Al(1) 2.085 0.535645 2.003674 1.974 2 9 1.951, 2.021, 3??-
Non-Loewenstein (NL) models
BRE49 Al(3) 1.776 0.508078 2.003624 1.904 2 9 1.895, 1.922, 3??*
BRE50 Al(3) 1.926 0.497070 2.003645 1.925 1.906, 2 9 1.935, 3*??
BRE51 Al(3) 1.748 0.521484 2.003628 1.888 2 9 1.869, 1.927, 3??*
a
for non-Loewenstein type (NL) models see please two Al–O and one Me–OAl2 distances and the Al–O–Al angle in Table 3; the notation
‘‘?’’corresponds to the ‘‘Mg cation–oxygen atom of the Si–O–Al type,’’ while the ‘‘-’’and ‘‘*’’ are related to Mg cation coordinated with oxygen
atom in the Si–O–Si and Al–O–Al species, respectively
b
Mg is not coordinated to Al–O*–Al species, |Mg…O*| = 5.024 Å

Al–O–Al as ‘‘*,’’ are shown in Fig. 2. The 3??* (Fig. 2e)
or 3*?? types of the Mg-coordination dominate in the NL
group. The ‘‘3??*’’ type denotes that two closest O1 and
O2 atoms near Mg cation are of the Si–(Mg)Oi–Al type
(Fig. 2a), i = 1, 2, and only the third nearest O3 atom is of
the Al–(Mg)O3–Al type (Fig. 2c). Respective distances
satisfy the sequence |Mg–O1| \ |Mg–O2| \ |Mg–O3|, and
the next nearest O4 atom is located outside radius of 3 Å
from the Mg atom. The ratio between the Mg–OAl2 and
Mg–OSiAl bond lengths in the 3??* or 3*?? groups
depends on each PHI or BRE model. Main geometric dif-
ferences between the LT and NL models are as follows:
(a) the shorter average Mg–O bond length Rav =
(Ri=1,n|Mg–Oi|)/n and (b) the smaller coordination number
n in the NL case (n = 3) than that in the LT ones (n = 4 or
5). The Rav decreases due to shortening of all the Mg–O
distances including the O?, O-, and O* types. The Rav
difference between LT and NL models is similar to the
difference of 0.09 Å between the Mg ionic radii corre-
sponding to n = 4 and 5 (Larin et al. 2005). As the zeolites
are semi-ionic frameworks, the idea of ionic radii is rele-
vant here so that the smaller NL coordination number 3 is
partly responsible for their shorter bond lengths. Unfortu-
nately, no data were shown in (Shannon 1976) for Mg if
n = 3.
The zeolite ionicity can be crudely evaluated via the
calculated Mulliken O charges. Additionally, regarding the
close O charges in any O?, O-, or O* positions (Fig. 2) in
LT and NL cases, no essentially higher Coulomb interac-
tions could be predicted for NL systems as compared to
those in LT ones. The Mulliken O charges for coordinated
Al–O(Mg)–Si, Al–O(Mg)–Al(Mg) and non-coordinated
Al–O–Si, Si–O–Si types are pretty close, being -1.153,
-1.174, -1.036, and -1.004 e, respectively, in the NL
type (BRE51). The O charges in the LT zeolite (PHI32) are
nearly the same for coordinated Al–O(Mg)–Si, Si–O(Mg)–
Si, and non-coordinated Al–O–Si, Si–O–Si moieties, being
-1.153, -1.146, -1.029, and -1.011 e. The absolute O
charges in the Si–O–Si or Al–O–Si species thus grow
similarly as much as by 0.1 e upon Mg-coordination.
Important consequence of the interaction between
divalent cation and the T–O–T’ groups, T or T’ = Al or Si,
is the correlation between the Rav and the cell electron
kinetic energy (Fig. 3a) and between the Rav and the Upot/
Ukin ratio (Fig. 3b, S1). The Upot/Ukin ratio or virial ratio
(VR) should be equal to -2 in equilibrium system as
determined by virial theorem. Respective energy should be
calculated at the same computational level, which is
applied to fully optimize unit cell geometry. As demon-
strated (Figs. 3b, S1), the VR for both LT and NL remains

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Phys Chem Minerals
Fig. 2 The types of O atoms: a Si–O–Al or ‘‘?,’’ b Si–O–Si or ‘‘-,’’
c Al–O–Al or ‘‘*,’’ and two examples of the Mg connections to the
nearest O atoms d 4???? in MgBRE6 and e 3??* in MgBRE51.
The color code is as follows: O in red, Si in yellow, Al in violet, Mg in
green
close to -2. The potential/kinetic ratio is, however, sys-
tematically lower in absolute value for NL type models
(Figs. 3b, S1). The only PHI12 model with the higher (in
absolute value) VR ratio of -2.0036661 (Table 2)
throughout all the NL group deviates from this trend.
However, it does not contain the Mg–OAl2 group, which is
typical for all ‘‘stable’’ NL zeolites, because of the remote
Mg location at 5.024 Å far from Al–O–Al oxygen
(Table 3). As a consequence of this long Mg–O* distance,
PHI12 is less stable (Fig. 3c) by around 95 kcal/mol
compared with the other NL zeolites (PHI10 and PHI26).
Hence, the PHI12 model is not a typical NL system, and
respective point should not be taken into account (open
circle with the highest Rav = 2.051 Å throughout all the
NL models in Fig. 3a–c).
Analogous less stable NL model BRE50 also exists in
the BRE group, i.e., destabilized as much by 15.3 kcal/mol
relative to the most stable NL type BRE51 model (Fig. 3c),
with the largest (in absolute value) VR = -2.003645. The
latter is comparable with that of the LT models, for
example BRE6 possesses VR = -2.003650 (Table 2). The
reason seems to be related to higher Rav (1.925 Å) in the
BRE50 case (Table 2). The two other NL BRE models
with average Mg–O distances of 1.888 and 1.904 Å possess
the smaller (in absolute value) VR of -2.003628 and
1
The VR value shifts the energy scale requiring at least 6 digits after
comma. This 6th digit corresponds nearly to 10-3 a.u. or 0.63 kcal/
mol. For the Utot, the third digit after comma corresponds to kcal/mol.
The validity of the digits of VR value is discussed below in the text.
-2.003624, respectively. But this explanation due to
higher Rav value is not totally justified because the PHI26
model of the NL type has larger Rav of 1.929 Å and smaller
(in absolute value) VR of -2.003632. Anyway, the BRE50
is much closer to the group of the NL points (open symbols
in left upper corner in Fig. 3a) with higher kinetic energy
than strongly destabilized PHI12 model.
The six digits used above (Table 2) in the VR values
could be questioned. Do our methods allow it? In order to
answer to the question, we have transformed the reliable
accuracy (1 kcal/mol) of the CRYSTAL code to the VR
scale. Finally, this accuracy depends on the basis set, but
we have tested the basis set for MgPHI as converged one
relative to further improvement (Larin et al. 2008), so that
such error of 1 kcal/mol is rather overestimated. We accept
this error for both Upot and Ukin energies. The VR value is
the potential energy divided by the kinetic energy. For
transformation of the energy error of 1 kcal/mol to the
scale of VR, we have considered the typical LT model
PHI11 with kinetic energy of 7227.2747 a.e. (Fig. 3a).
Then, we have evaluated the accuracy 1 kcal/
mol = 1.594 9 10-3 a.u. in the VR scale by dividing it by
Ukin. The accuracy in the scale of VR is 1.594 9 10-3/
7227.2747 = 2.2 9 10-7. So, the variation in seventh digit
in the VR value corresponds to the accuracy 1 kcal/mol
allowed by the CRYSTAL code. The usual differences in
the VR values between LT and NL models with B3LYP
(Table 2) range from 5 9 10-6 to 8 9 10-5 (omitting
much less stable PHI12 model) for the PHI zeolites and
from 5 9 10-6 to 6 9 10-5 for the BRE ones. Both values
are larger than the accuracy of 2.2 9 10-7 (dimension-
less) = 1 kcal/mol as presented in the same VR scale.
Hence, these small VR differences between LT and NL
models are valid.
Our result can signify that together with the energy gain
owing to higher potential energy between Mg and O*
atoms for NL systems, the Al–O(Mg)–Al groups lead to
higher average electron kinetic energy per cell. The strong
Mg–O interaction appears due to the shorter Mg–O dis-
tances with all oxygen types. Resuming these variations,
the total energy leads to less stable NL zeolites (Fig. 3c).
The higher relative stabilities of the LT than those of the
NL models hold at PHF level (see Table S3 in Supple-
mentary Materials). Hence, such behavior is not condi-
tioned by the B3LYP functional selected herein or any
other DFT functional. Earlier (Larin et al. 2005; Larin and
Vercauteren 2001), we have compared electron density
distributions and relative energies of H-form zeolite mod-
els using periodic boundary conditions at the PHF/STO-3G
level. In opposite to the bad experience with this basis set
for isolated cluster calculations, the coherent relative
energies have been obtained for proton positions with two
(STO-3G and ps-21G*) basis sets. Different order of the
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 Phys Chem Minerals

Fig. 3 Dependencies between (a) Rav and Ukin, (b) -Upot/Ukin and models of MgPHI (circles) and MgBRE (triangles). Correlation
Rav, (c) Upot/Ukin and Utot calculated at the (a–c) PDFT/B3LYP/85- coefficients are shown for PHI (dashed line) and BRE (dotted line) for
11G*(Mg, Al)/88-31G*(Si)/6-31G*(O) level for Loewenstein (LT, both LT and NL models and for all the models together (solid line)
closed symbols) and non-Loewenstein (NL, open symbols) type

Table 3 The parameters of non-Loewenstein (NL) models in MgPHI between the LT and NL models do not change. The poorer
and MgBRE zeolites optimized at the PDFT/B3LYP level with STO-3G basis set results in the larger VR deviation up to
85-11G*(Mg, Al)/88-31G*(Si)/6-31G*(O) level: Al–O distance (Å), -2.01 for optimized models than that obtained at the
Al–O–Al angle (degree), and Mg-OAl2 (or Mg–O*) distances (Å)
B3LYP/85-11G*(Mg, Al)/88-31G*(Si)/6-31G*(O) level, but
Type |Al–O| Al–O–Al |Mg–O*| VR is also larger (in absolute value) for LT models than for NL
PHI10 2 9 1.746 141.3 1.913 ones (Table S3, Fig. S1). Hence, the kinetic energy also larger
PHI26 2 9 1.745 142.1 1.915 for the NL type models at the PHF/STO-3G level.
PHI12 2 9 1.693 122.4 5.024
BRE50 2 9 1.739 140.1 1.906
Direct scaling of atomic wavefunction
BRE49 2 9 1.743 157.4 1.922
The minor deviation of the VR value versus -2 for the
BRE51 2 9 1.754 165.1 1.927
optimized system shows nevertheless that the basis set
could be improved looking for a proper scaling factor for
relative energies between these basis sets was obtained in all the atomic orbitals. Formally, we should have exact
one HNAT case throughout the series of five small size equation VR = -2 at the energy minimum with respective
zeolites. That is why these relative stabilities could also be optimal value of scaling a parameter. We tested some grids
discussed with STO-3G. from 5 to 7 points nearby the initial minimum position
Herein, despite some variations in the PHF optimized (a = 1) to evaluate the optimal value of scaling a param-
geometries and cation coordinations, the main differences eter. First, parabolic approximations over 5 and 7 points

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Phys Chem Minerals
Table 4 Energy values (a.u.) and VR using different scaling of wave
functions, i.e., at the minimum of parabola fitted via 5 or 7 points,
along with scaling parameter a for some LT (PHI11, PHI21) and NL
(PHI26) models (see text for details)
Model -U/-VR
7 (a = 1.00123) 5 (a = 1.00103)
PHI11 7253.563653/2.00175 7253.564003/2.00206
PHI21 7253.565200/2.00177 7253.565586/2.00207
PHI26 7253.521828/2.00175 7253.522196/2.00204
were applied with grid step Da = 0.01 and very high
correlations for both cases (Table 4, five points were
obtained from seven simply omitting two extreme points).
The grids of 5 points led to deeper energies at parabola
minimum values being close nevertheless to a = 1.001 in
both cases (5 or 7 points). So, we have selected a grid with
smaller step Da = 0.005 around a = 1.001 for total
comparison of the cell energies after rescaling. Relative to
the grid Da = 0.01 with the average parameter error
ranging between 0.3 and 0.4 %, the new grid results in the
smaller parameter errors near 0.2 %. One has to note that
the total energy difference between 5- and 7-point grids is
minor, i.e., 0.2 kcal/mol between both energies corre-
sponding to the parabola minimum.
In such a way, we have obtained the corrected energy
minimum for some PHI models (Table 4) with slightly
different a-coordinates for each parabolic approximation.
Respective energy components do not satisfy to exact
equation VR = -2 at the minimum being smaller in
absolute value but nearly -2.002 (Table 4) instead of
-2.0037 or -2.0036 without scaling (Table 2). The energies
of the corrected models calculated with scaled functions
can only be compared at the same a-value, for example at
two a values fitted over 5 (a = 1.00103) or 7
(a = 1.00123) points (Table 4). Respective energies
demonstrate that the a-scaling procedure does not invert
the relative stabilities of LT and NL models. The VR value
after scaling can also be compared to that obtained with the
minimal STO-3G basis set, i.e., between -2.0115 and
-2.0104 (Table S3) at the PHF level. We suppose that the
VR deviation from -2 can be deleted while optimizing the
zeolite models with more accurate basis set, for example,
using iteratively the scaled functions.
Ideal scaling procedure formally does not allow dis-
cussing the variations of the kinetic energies between dif-
ferent zeolites, because if exactly VR = -2, then more
stable zeolite model has higher kinetic energy. In such a
situation, the points of more stable LT models in Fig. 3a
should be located above the NL ones, while they are now
below with the exception of the most stable PHI11 model.
The latter has the highest Ukin according to its highest Utot
(in absolute value). Our NL and LT models have inverse
ratio with lower kinetic energy for more stable LT models
(Fig. 3c). This situation was not changed herein with the
scaling performed above. The conservation of the higher
stability of LT models versus NL ones after scaling
approves the connection proposed herein between the sta-
bility and electron kinetic energy.
Evaluations of entropy differences between LT and NL
models
Finally, the enthalpy gain DH is larger for LT than for NL
models as shown above (Table 2, Table S3), i.e., the
enthalpy differences between the most stable LT and NL
models range from 30.3 kcal/mol (between PHI11 and
PHI26) to 36.8 kcal/mol (between BRE6 and BRE51). In
order to evaluate the Gibbs energy variation DG = DH
- TDS for LT and NL models, one needs their entropy
values. Two main configurational and vibrational compo-
nents can be separated. It is easy to calculate that the
configurational entropy term –TDS in the Gibbs energy
will be larger (in absolute value) for LT models. It is a
consequence of the wider set of all possible types of Al
distributions in the LT zeolite lattice compared to the NL
models. For the case of the BRE framework with 12 Si and
4 Al positions, this configurational entropy difference can
be easily estimated taking into account spatial P21/m
symmetry group, which simplifies the task. The BRE cell
skeleton is partitioned into two symmetric parts each
containing 6 Si and 2 Al positions (Fig. S2). So, it is
enough to distribute the Al atoms in the one of two sym-
metric parts. The LT degeneracy to distribute Al atoms
without Al–O–Al species is the probability for the first Al
atom to occupy any of 8 sites and for the second Al one to
occupy any of five remaining sites around because of one
occupied and two forbidden sites, i.e., 8 9 C15 = 8 9 5!/
4! = 40. Analogous NL degeneracy is the probability for
the first Al atom to occupy any of 8 sites and for the second
Al any of two remaining sites around, i.e., or 8 9 C12 = 16.
Then, the probability ratio 40/16 = 2.5 is the consequence
of the P21/m symmetry and BRE structure. Then, this
contribution to the Gibbs energy difference between LT
and NL models is T 9 DS = T 9 k9N0 9 ln(40/16) =
T 9 1.38 9 10-23 9 6.02 9 1023 9 0.916 = 7.61 9 T J/
(K 9 mol), where k is Boltzmann constant, N0 is Avogadro
number. At room temperature, respective term gives
2.44 kJ/mol = 0.58 kcal/mol in favor of the LT model.
Hence, the total Gibbs energy will be larger in absolute
value for the LT zeolites due to the configurational entropy.
Due to the same P21/m symmetry and content (Table 1),
the same estimations are valid for PHI zeolite. This small
value cannot play significant role for the total Gibbs energy
difference between LT and NL models compared to the
123

enthalpy difference around 30 kcal/mol or 0.05 a.u. men-
tioned in the beginning of this part (Table 2). Evidently,
this configurational TDS difference will grow with Si/Al
ratio.
The small configurational entropy contribution to the
Gibbs energy -TDS shows that vibrational entropy is the
main part of the total entropy. The latter can be directly
obtained with the CRYSTAL code after full optimization
and frequency calculation. This permits to have the -TDS
difference between LT and NL models. The calculated
frequencies are presented for two typical LT (PHI11,
PHI21) and one NL (PHI26) models in Table S4. One
should note that three (PHI11) or four (PHI21 and PHI26)
imaginary frequencies are obtained. Three values for each
model from 3i to 6.1i cm-1 (not shown in the Table S4)
correspond to three translational modes of the center of
mass motions that can be neglected. Imaginary frequency
of 41i cm-1 (PHI21) and 199i cm-1 (PHI26) for two
models corresponds to the low-frequency framework
vibration (see 41i.mpg or 199i.mpg animation files in
Supplementary Materials) and formally should be recal-
culated using algorithm to improve the geometry. The
small real frequency value for respective vibration follows
the large size of vibrating fragments. However, these
vibrations do not involve the geometry variation of the
MgOAl2 groups that participate as whole components with
fixed Mg–O and Al–O distances (please, see animation
files in Supplementary Materials). Hence, omitting one
frequency in the whole series is not very important for the
entropy difference between LT and NL groups (Table 5).
Additional reason to not re-calculate the vibrational profile
is related to the minor TDS0 variation (1.8 kcal/mol)
between PHI21 (-90.6 kcal/mol with all one imaginary
frequency) and PHI11 (-92.4 kcal/mol with all real fre-
quencies). That is why we did not convert two imaginary
frequencies to real values using the CRYSTAL facilities
(they are omitted when calculating the entropy).
Calculated entropies S0 and the Gibbs energy part
-TDS0 at room temperature and standard pressure for LT
and NL models are shown in Table 5. They can be com-
pared to known experimental value for hydrated
K1.6Na2.16Al3.76Si12.24O32 9 12H2O phillipsite (Vieillard
Table 5 Cell volume V (Å3), standard entropy S0 for dehydrated
forms (in cal/mol/K), corrected entropy S0H = S0 + 12S0H2 O (S0H2 0 ¼
12:98cal/mol/K (Vieillard 2010)) for hydrated forms, -TS0 (in kcal/mol)
Model Type V S0
PHI11 LT 926.7
PHI21 LT 924.6
PHI26 NL 966.5
Experiment 996.7 (Hemingway and Robie 1984)
123
Phys Chem Minerals
2010), considering standard entropy of zeolitic water
S0H2O = 12.98 cal/mol/K (Vieillard 2010). This allows the
direct comparison just adding to the values for dehydrated
models (column S0 in Table 5) the total entropy of twelve
water molecules or 155.8 cal/mol/K (column S0H in
Table 5). In such a way, we obtained underestimated (in
absolute value) values for both LT and NL models by
around 15–18 %. The underestimation is partly explained
by the smaller volume of dehydrated theoretical models
whose contraction around some percent upon dehydration
is well known (Larin et al. 2003). This error of 15–18 %
should be considered as satisfactory one, regarding: (1)
different cationic content in (Vieillard 2010), and herein,
(2) harmonic approximation applied to calculate the par-
tition functions. In some sense, such harmonic approach
applied to calculate entropy is in a contradiction with high
temperature area where the entropy term can be more
important. At high temperatures, anharmonic potentials
should be used instead of the harmonic ones. However,
such estimation of partition functions for solids is not yet
realized to our best knowledge requiring models that vary
with temperature for computed energy surfaces. Their
temperature boundaries have to be found regarding the
mobilities of various zeolite groups and checking the
possible coupling between them. The difference TDS0
obtained with harmonic approximation using the CRYS-
TAL code between the LT and NL models does not exceed
2.5 kcal/mol so that we believe that the enthalpy is the
main term, which determines the favored Gibbs energy for
LT species.
Discussion
Dominating role of kinetic energy for chemical bond for-
mation in molecules was first discussed by Rudenberg et al.
in a series of publications beginning from 60th years
(Ruedenberg 1962; Feinberg and Ruedenberg 1971a, b;
Ruedenberg and Schmidt 2007). In his turn, Rudenberg
addressed to the Hellman’s model of bond formation in
H2? ion owing to the decrease in kinetic energy upon
electron orbital sharing (Hellmann 1933). The energy gain
values, and the errors of the TS0H calculation (in %) for LT (PHI11,
PHI21) and NL (PHI26) forms
S0H -TS0H Error
154.1 309.9 -92.4 15.9
148.0 303.8 -90.6 17.6
156.5 312.3 -93.1 15.3
– 368.7 (Vieillard 2010) -109.9 (Vieillard 2010) –
Phys Chem Minerals
happens owing to a longer potential box for electrons in the
direction along with the molecular H2? axis (see Fig. 1 and
Table 1 in (Feinberg and Ruedenberg 1971a). The funda-
mental conclusion about the reason for bond formation was
expanded from diatomic homonuclear (Feinberg and Rue-
denberg 1971a) to heteronuclear (Feinberg and Ruedenberg
1971b) molecules regarding exceptionally variational
approach. All the examples in (Ruedenberg 1962; Feinberg
and Ruedenberg 1971a, b; Ruedenberg and Schmidt 2007)
were discussed for isolated molecules. The authors (Rue-
denberg 1962; Feinberg and Ruedenberg 1971a, b; Rue-
denberg and Schmidt 2007) considered different trial
wavefunctions and showed that decrease in kinetic energy
does not depend on the basis set. In this respect, we have
tested two basis sets and have obtained similar results with
both of them. We have considered the case of periodic NL
systems which cannot be formed due to the increase in
kinetic energy, if a special defect, i.e., the Al–O(Mg)–Al
species, is present in the zeolites. We suppose that the
Loewenstein rule (Loewenstein 1954) is explained at least
partly by this destabilization due to the increase in kinetic
energy in the semi-ionic systems. One of the reasons for the
increase is the shorter Mg–O bonds in the NL type zeolites.
We suppose that the shorter bonds in solids can be a factor
of its lower stability as could be deduced from results of
(Freysoldt et al. 2011). But, important contribution of
kinetic energy for an interstitial defect site in GaAs (Fig. 8
in ref. (Freysoldt et al. 2011) is assigned to the electrostatic
energy due to self-consistent character of the calculation.
From other theories that showed the growth of kinetic
energy at the shorter bond length, one should mention
‘‘atoms in molecules (AIM)’’ (Espinosa et al. 1998). But
electron kinetic energy is related to the critical points of
hydrogen bonds so that the impact on the total energy of
whole system was not calculated.
Conclusions
The divalent (Mg) cationic forms were selected for the
stabilization of the Al–O–Al groups in two different PHI
and BRE zeolite frameworks. The energy of fully opti-
mized MgPHI and MgBRE forms, which include Al–O–Al
moieties (non-Loewenstein or NL types) or do not (tradi-
tional Loewenstein type or LT), is calculated at the hybrid
density functional theory level with periodic boundary
conditions. The following conclusions can be formulated:
(1) the total energies of the LT types are higher in absolute
values than that of the NL ones. This demonstrates a
thermodynamic nature of the lower stability of NL zeolites
containing Al–O–Al moieties in agreement with the con-
clusions (Catlow et al. 1996); (2) the presence of the Mg–
OAl2 groups in the NL frameworks results in higher kinetic
energies relative to the similar values in the LT series; (3)
the relative stabilities of LT and NL types do not invert
upon scaling of wavefunction; (4) the virial ratio is close to
-2 as determined with virial theorem that was not yet
shown numerically for DFT in a periodic case as herein; (5)
the decrease in kinetic energy was carefully analyzed to be
the main reason for bond formation in isolated ions and
molecules from atoms (Ruedenberg 1962; Feinberg and
Ruedenberg 1971a, b; Ruedenberg and Schmidt 2007;
Hellmann 1933). Analogous phenomenon of instability in
periodic NL zeolite systems due to the increase in kinetic
energy is observed herein, if a special defect, i.e., the Mg–
OAl2 species with shortened inter-atomic distances, is
presented in the NL zeolite. Finally, we conclude that bond
shortening produces the total energy loss for the NL
models. It could be a relevant problem for the formations
of interstitial defects with short inter-nuclear distances in
solids.
Supplementary Materials
Analogous computations for the same models performed at
the periodic Hartree–Fock (PHF) level with minimal STO-
3G basis set are given in Supplementary Materials to
illustrate the same relative behavior of the LT and NL
models at the pure Hartree–Fock level. They contain three
Tables which are similar to the Tables 1–3 at PHF com-
putational level, one Table with calculated frequencies, and
two Figures. Animation files 199-b.mpg and 41i.mpg
demonstrate vibrational modes of PHI26 and PHI21 mod-
els with the imaginary frequencies of 199i and 41i cm-1,
respectively, discussed in the part ‘‘Evaluations of entropy
differences between LT and NL models’’.
Acknowledgments The author is indebted to Dr. V.I. Pupyshev for
the stimulating discussions and propositions, to Prof. D.P. Vercaut-
eren and Dr. A.A. Rybakov for permanent help, and to Mr. D.M.
Kovtun for the references to the publications of K. Rudenberg et al.
and for his interest in our work. The author thanks the financial
support of Ministry of Education and Science of Russian Federation
(Minobrnauka, GK No 07.514.11.4150). The author acknowledges
the FUNDP, F.R.S.-FRFC (convention 2.4.617.07.F) for the use of the
Namur Interuniversity Scientific Computing Facility Centre (Bel-
gium) and Computer Complex SKIF of Moscow State University
‘‘Lomonosov’’ and ‘‘Chebyshev’’ for computational time. RFFI is
deeply acknowledged for the grant 12-03-00749a.
References
Catlow CRA, George AR, Freeman CM (1996) Chem Commun
11:1311
Catti M, Civalleri B, Ugliengo P (2000) J Phys Chem B 104:7259
Cormier L, Ghaleb D, Neuville DR, Delaye J-M, Calas G (2003) J
Non-Cryst Solids 332:255
123

Dempsey E (1974) J Catal 33:497
Dovesi R, Saunders VR, Roetti C, Orlando R, Zicovich-Wilson CM,
Pascale F, Civalleri B, Doll K, Harrison NM, Bush IJ, D’Arco P,
Llunell M (2006) CRYSTAL06 User’s Manual. University of
Torino, Torino
Engelhardt G, Lohse U, Lippmaa E, Tarmak M, Mägi M (1981) Z
Anorg Allg Chem 482:49
Espinosa E, Molins E, Lecomte C (1998) Chem Phys Lett 285:170
Feinberg MJ, Ruedenberg K (1971a) J Chem Phys 54:1495
Feinberg MJ, Ruedenberg K (1971b) J Chem Phys 55:5804
Freysoldt C, Neugebauer J, Van de Walle CG (2011) Phys Stat Sol B
248:1067
Gonzalez-Gallardo S, Jancik V, Delgado-Robles AA, Moya-Cabrera
M (2011) Inorg Chem 50:4226
Hellmann H (1933) Z Phys 35:180
Hemingway BS, Robie RA (1984) Am Mineral 69:692
Larin AV, Vercauteren DP (2001) J Mol Cat A 168:123
Larin AV, Trubnikov DN, Vercauteren DP (2003) Int J Quantum
Chem 92:71
Larin AV, Parbuzin VS, Vercauteren DP (2005) Int J Quantum Chem
101:807
Larin AV, Sakodynskaya IK, Trubnikov DN (2008) J Comput Chem
29:2344
123
Phys Chem Minerals
Lee SK, Stebbins JF (2000) J Non-Cryst Solids 270:260
Loewenstein W (1954) Am Mineral 39:92
Melchior MT, Vaughan DEW, Jacobson AJ (1982) J Am Chem Soc
104:4859
Mikovsky RJ, Marshall JF (1976) J Catal 96(44):170
Mikovsky RJ, Marshall JF, Burgess WP (1979) J Catal 58:489
Pelmenschikov AG, Paukshtis EA, Edisherashvili MO, Zhidomirov
GM (1992) J Phys Chem 96:7052
Pingel U-T, Amoureux J-P, Anupold T, Bauer F, Ernst H, Fernandez
C, Freude D, Samoson A (1998) Chem Phys Lett 294:345
Ramdas S, Thomas JM, Klinowski J, Fyfe CA, Hartman JS (1981)
Nature 292:228
Rinaldi R, Pluth JJ, Smith JV (1974) Acta Cryst B 30:2426
Ruedenberg K (1962) Rev Mod Phys 34:326
Ruedenberg K, Schmidt MW (2007) J Comput Chem 28:391
Schlenker JL, Pluth JJ, Smith JV (1977) Acta Cryst B 33:2907
Shannon RD (1976) Acta Cryst A 32:751
Sykes D, Kubicki JD (1996) Am Mineral 81:265
Vieillard P (2010) Eur J Miner 22:823
Zhao P, Neuhoff P, Stebbins JF (2001) Chem Phys Lett 344:325