17548 J. Phys. Chem.

C 2009, 113, 17548–17559

An Investigation of Distortions of the Dion-Jacobson Phase RbSr2Nb3O10 and Its

Acid-Exchanged Form with 93Nb Solid State NMR and DFT Calculations

Xuefeng Wang, Jhashanath Adhikari, and Luis J. Smith*

Carlson School of Chemistry and Biochemistry, Clark UniVersity, 950 Main Street,
Worcester, Massachusetts 01610
ReceiVed: March 15, 2009; ReVised Manuscript ReceiVed: July 19, 2009

The different niobium sites in a Dion-Jacobson triple-layered perovskite, RbSr2Nb3O10, and its acid-exchanged
version, HSr2Nb3O10, were investigated by using solid state NMR and DFT methods. 93Nb electric field gradient
(EFG) and chemical shift anisotropy (CSA) tensor values were extracted and site assignments made by using
DFS, VOCS, MQMAS, and {1H}-93Nb CP NMR techniques. The exterior niobium site exhibited a quadrupolar
coupling (CQ) of 45 MHz and a CSA span of 820 ppm while the interior site exhibited a reverse trend with
a CQ of 93 MHz and a CSA span of 530 ppm. Both EFG and CSA tensors for the sites exhibited near axial
symmetry although the CSA tensors had a greater deviation. The symmetry of the tensors is in conflict with
the previously proposed structure for RbSr2Nb3O10 and implies a lower symmetry space group and a possible
tilting of the octahedra. Acid exchange altered the EFG tensors for both sites reducing their CQ values to 39
and 86 MHz, respectively, while not substantially changing the tensor symmetry. The effect on the CSA
tensor occurred only for the surface site with the span reduced to 560 ppm. The effect of the tilting of the
octahedra and alteration of bond angles and bond lengths on the EFG tensor was investigated through periodic
DFT calculations. Interior and exterior sites of the rubidium form exhibited different tilt along the c-axis of
14° and -3°, respectively, based on the 93Nb EFG values. Calculations on the acid-exchanged composition
implied that structural alterations must occur with both sites. The exterior octahedra experience changes in
both bond length and bond angles, while only a subtle elongation of the interior site is found.

Introduction
Lamellar oxides have a large variety of compositions and
possible structures that leads to diversity in the properties of
these materials. Many systems of interest have niobium as a
six-coordinate metal in the oxide lattice. In several of these
layered niobates, photocatalysis,1,2 superconductivity,3,4 and
proton conduction5 have been observed. Exfoliation of these
layered compounds further expands the potential uses. Several
exfoliated layered niobates have been explored as photocatalysts,6,7
solid acid catalysts,8-11 and nanosheet building blocks for more
complex oxide thin films.12,13 In many cases, the details of
structural perturbations or variations that occur with differences
in composition or postsynthetic treatment are not well-known.
X-ray diffraction methods lose resolution when the particle size Figure 1. Crystal structure of RbSr2Nb3O10, at left (niobia octahedra,
or domain size decreases after exfoliation or exfoliation followed green; strontium, blue; rubidium, pink), and subsection, at right, of a
by restacking.14-16 However, through element-selective spec- single triple-perovskite layer with the interior, Nb1, and exterior, Nb2,
troscopic methods such as NMR, the distortions that are present sites labeled.
in the local environment of the metal sites can be determined
even when sufficient long-range order of these distortions is series of these layered perovskites follow the general formula
not present. As acid exchange is the first step in the exfoliation of A[A′k-1BkO3k+1], where k equals the number of octahedra
process used to produce nanosheets from these layered niobates, stacked within a slab. The flexibility of the properties of these
understanding what structural changes occur in this step is materials comes with the wide range of elements that can serve
important for understanding any properties derived from these as the A and B cations. As with three-dimensional perovskites,
nanosheets or the novel thin films built from them. often the A and B cations are not of a sufficient size to fill the
One family of lamellar oxides is based on the perovskites octahedral holes present in the oxide lattice. With smaller B
structure. Corner sharing BO6 octahedra are interleaved with A cations, the result is often a displacement from the center of
cations and form a two-dimensional pervoskite slab (Figure 1). the octahedron. Small interstitial A cations can distort the oxide
The negatively charged layers are interleaved with a second lattice resulting in a pattern of tilting for the BO6 octahedra.
set of cations that are ion-exchangeable.17-20 The Dion-Jacobson The Dion-Jacobson layered perovskites can have these distor-
tions. The exterior octahedra at the interface between layers in
* To whom correspondence should be addressed. E-mail: lusmith@ KCa2Nb3O10 and CsCa2Nb3O10 have displaced niobium atoms
clarku.edu. resulting in an effectively five-coordinated site and are canted
10.1021/jp902318v CCC: $40.75  2009 American Chemical Society
Published on Web 09/11/2009
Distortions of the Dion-Jacobson Phase RbSr2Nb3O10
with respect to each other and the interior octahedra.21,22 The
interior octahedra do not have displaced B cations but are tilted
with respect to each other. The small size of the Nb5+ and Ca2+
cations leads to these distortions. Previous X-ray powder
diffraction studies of RbSr2Nb3O10 suggest that the larger
strontium cation does not perturb the oxide lattice leading to a
highly symmetric structure.23 While no tilting is present, the
displacement of the niobium atoms in the exterior octahedra is
still observed. Calculation of the polyhedral volume ratio for
Sr2+ and Nb5+ and the tilt angle derived from it shows that a
tilt would be expected in a three-dimensional perovskite with
these cations.24 Recent Raman spectroscopy studies have
suggested that the layered structure does indeed have a tilt
present.25 However, the interpretation of Raman spectra is
difficult as the technique observes the whole structure and does
not easily permit the interpretation of the effect of distortions
on the individual octahedra.26,27
NMR is well suited for the examination of the local
environment of the niobium atom at the center of the octahedron.
With this specific focus, the changes in coordination and bond
length that come with the distortions possible in perovskites
can be quantified. The NMR parameters determined can be
directly linked to the crystal structure through the use of
quantum mechanical calculations. Furthermore, density func-
tional theory (DFT) calculations that incorporate periodic
boundary conditions enable a more thorough determination of
interactions that have long-range contributions such as the
electric field gradient (EFG) experienced at the metal site.28-33
The EFG is a particularly relevant descriptor of metal sites as
many inorganic materials incorporate quadrupolar nuclei. These
are nuclei with nuclear spins greater than 1/2 and constitute about
75% of the NMR observable nuclei. As a result, methods applied
to these nuclei can be useful in numerous oxide systems.
Additional interactions with the field created by the local
bonding electrons are manifested in the chemical shift anisotropy
(CSA), which is dependent on the local symmetry of the metal
site. CSA is potentially present for all nuclei, quadrupolar or
not, but can vary in magnitude depending on the element.
Both EFG and CSA interactions lead to anisotropies that
affect the shape of the powder distribution observed in NMR
experiments. The EFG tensor can be described by three
components VXX, VYY, and VZZ in its own principal axis system
(PAS). The terms are typically defined such that |VXX| e |VYY|
e |VZZ| and VXX + VYY + VZZ ) 0. Two independent terms result:
the quadrupolar coupling, CQ ) eQVZZ/h, where Q is the
quadrupolar moment, and the asymmetry parameter, η ) (VXX
- VYY)/VZZ with values ranging from 0 to 1.34 The CSA tensor
is described by three components in its respective PAS: δ11,
δ22, and δ33. The tensor components are combined together to
yield three descriptive parameters: the isotropic chemical shift,
δISO, the span, Ω, and the skew, κ. The span of the CSA is
defined by Ω ) δ11 - δ33, and represents the magnitude of the
anisotropy. The skew is defined by κ ) 3(δISO - δ22)/Ω, and
represents the symmetry of the tensor with values ranging from
-1 to 1.35 As each tensor is defined within its own PAS, a set
of Euler angles, R, β, and γ, which define their relative
orientation, is needed to relate the direction of one tensor in
terms of the other.
The NMR active isotope for niobium, 93Nb, has a NMR spin
of 9/2 and has 100% natural abundance making it extremely
useful for these studies. The size of the quadrupole moment of
93
Nb is large enough that the EFG interaction in most materials
is best described by a second-order quadrupolar interaction.36,37
As a result, most NMR investigations focus on the central
J. Phys. Chem. C, Vol. 113, No. 40, 2009 17549
transition, -1/2 T 1/2, as the other transitions are too broad for
convenient observation. Magic angle spinning (MAS) can reduce
the impact of the anisotropies on the observed line shape by
completely averaging the effect of the CSA and partially
averaging the effect of the EFG if the spinning speed exceeds
the magnitude of the CSA. As a result, line shapes observed
under static conditions contain both CSA and EFG tensor
information while MAS based experiments can be made to yield
only EFG tensor values and the isotropic chemical shift.38
Assisting with the extraction of the tensor values is the different
field dependencies of the interactions. The CSA interaction is
proportional to the magnetic field strength, and the EFG
interaction is inversely proportional, when second-order interac-
tions are present. Thus a combination of multiple magnetic fields
and static and MAS experiments can extract the values of the
two tensors and their relative orientations. With 93Nb nuclei,
both the EFG and CSA can have large magnitudes that require
this multiple experiment approach. The CSA and EFG are
sufficiently large enough that normal MAS methods do not
suffice and two-dimensional rotor-synchronized multiple quan-
tum MAS (MQMAS) experiments are required.39,40 Rotor-
synchronization along with an alternate shearing scheme for
processing the two-dimensional data (vide infra) make it possible
to extract the EFG values without the influence of CSA and
are crucial to this study.
In this study, the structure of the Dion-Jacobson layered
perovskites, RbSr2Nb3O10, is examined via 93Nb NMR to
examine the extent of structural distortion present. Furthermore,
the effect of acid exchange, a precursor to exfoliation, is
measured. The EFG and CSA tensor information for the niobium
sites is determined by using multiple magnetic field, wide-line
experiments and MQMAS experiments at moderate field
strengths. The approach utilized was able to extract EFG and
CSA information despite the substantially large values for both.
The NMR tensor information is related to the possible structures
for the compounds based on symmetry arguments and DFT
calculations. Both possible tilt angles and structural rearrange-
ments are predicted based on the NMR and computational
results.
Experimental Section
1. Synthesis. The RbSr2Nb3O10 sample was prepared via
microwave heating. A ground mixture consisting of RbNO3,
SrCO3, and Nb2O5 with a molar ratio of 1.25:2:3 for Rb:Sr:Nb
was used. The sample was heated with use of silicon carbide
susceptors in an insulated thermal box (EPL Ceramic Materials)
in conjunction with a 1200 W domestic microwave oven at 90%
power for 5-10 min followed by 50% power for 10-15 min.
The product was then washed with distilled water and dried.
To produce the acid forms, the parent compound was treated
with 6 M HNO3 for 3 days at 80 °C. Each day the acid solution
was replaced. After acid exchange, the product was filtered,
washed with distilled water, and dried at 130 °C.
2. X-ray Diffraction. All powder diffraction data were
collected with a Bruker AXS D8 Focus diffractometer, using
Cu KR radiation. Powder diffraction was used to determine the
phase identity of the samples after synthesis or postsynthetic
processing. Whole pattern fitting was conducted by using the
LeBail method in conjunction with the TOPAS software
suite.41,42
3. Solid State NMR Spectroscopy. The 87Rb MAS spectrum
was collected at a field strength of 9.4 T, using a resonance
frequency of 130.81 MHz. Data were collected with use of a
2.5 mm double resonance MAS probe with a spinning rate of
17550 J. Phys. Chem. C, Vol. 113, No. 40, 2009
20 kHz. A Hahn echo pulse sequence using π/2 and π pulse
lengths of 2 and 4 µs with a recycle delay of 0.8 s was used.
All 87Rb chemical shifts are reported relative to a 0.5 M aqueous
RbNO3 solution (0 ppm).
All 93Nb NMR data were collected at magnetic field strengths
of 9.4 and 14.1 T on Unity INOVA spectrometers with resonance
frequencies of 97.74 and 146.75 MHz, respectively. A 2.5 mm
double resonance MAS probe was used for all experiments on the
9.4 T instrument. Experiments on the 14.1 T instrument utilized a
5 mm triple resonance liquid state probe. Variable offset cumulative
spectra (VOCS)43 echo data were constructed from 15 Hahn echo
spectra collected with an offset difference of 78.125 and 62.5
kHz, using a radio frequency field strength of 20 and 11 kHz
for the 9.4 and 14.1 T spectrometers, respectively. Incomplete
double frequency sweeps (DFS) in conjunction with the VOCS
method were used on both instruments for selective enhance-
ment of small EFG environments for spectral editing purposes.44
The frequency sweep was placed before the Hahn echo pulses.
The DFS pulse had a start frequency of 650 kHz and final
frequency of 250 kHz with a radio frequency field strength of
20 and 10 kHz for the sweep for the 9.4 and 14.1 T
spectrometers, respectively. The start frequency was selected
based on the size of the quadrupolar coupling of the site of
interest. The final frequency was selected so that the sweep
ended before covering the central transition line shape. The Hahn
echo pulses had the radio frequency field strengths as the normal
VOCS echo experiment. An adiabaticity parameter45 of 0.32
was used for both sweeps. The resulting difference spectrum
resulted from the subtraction of the normal VOCS spectrum
from the VOCS spectrum created by the incomplete DFS
experiment. The static cross-polarization (CP) experiments were
collected at 9.4 T, using a 1H resonance frequency of 399.76
MHz, and the VOCS method was used to construct the final
spectrum with an offset difference of 39.0625 kHz and utilized
radio frequency strengths of 13 kHz for 93Nb and 65 kHz for
1 gradient approximation (GGA) in the parametrization of Perdew,
H with a contact time of 2 ms. All spectra were referenced to
NbCl5 in acetonitrile (0 ppm).
3QMAS experiments were conducted with use of a FAM-II
conversion pulse46 and a selective π pulse to generate a shifted
echo to ensure whole echo data collection. A 96-step phase cycle
following the +3Q f +1Q f -1Q pathway was used to
acquire the echo coherence transfer pathway only. An excitation
pulse of 1.7 µs and a four-pulse FAM-II sequence with pulse
lengths of 0.5 and 0.3 µs were used with a radio frequency field
strength of 85 kHz. The selective π pulse had a length of 2.0
µs, using a radio frequency field strength of 50 kHz. The dwell
time in the indirect dimension was set to ensure rotor-
synchronized conditions. A MAS rate of 28.5 kHz was used.
Eight data points were collected in the indirect dimension. A
spectral window of 400 kHz was used in the direct dimension.
An alternative shearing scheme was used to represent the 2D
rotor synchronized data in a fashion more amenable to the large
chemical shift range of 93Nb. The method used is based on an
approach outlined by Gan.47 An initial shearing transformation
using a coefficient of 3 as opposed to 91/36 was used to
eliminate the chemical shift contribution in the indirect dimen-
sion. An additional shearing transformation was then applied
to the data to rotate the quadrupolar anisotropy to lie along the
indirect dimension only. As a result, the first dimension only
contains anisotropy information related to the second order
quadrupolar interaction under MAS conditions. Since the
indirect dimension is rotor synchronized, all chemical shift
anisotropy information in this dimension has been removed. The
direct dimension now only contains isotropic chemical shift and
Wang et al.
quadrupolar shift information divided among isotropic sidebands
if the original anisotropies were too large to be averaged by
MAS. In the new scheme, the following relations (for I ) 9/2)
describe the frequencies in each dimension:
648 0
δ1(θ, φ) ) δ + 432 · δQ4(θ, φ) · P4(cos β) (1)
17 Q
648 0
〈δ1〉 ) δ (2)
17 Q
10
δ2 ) δCS
0
- 〈δ 〉 (3)
27 1
where δQ0 is the quadrupolar shift defined as δQ0 ) -[CQ2(3 +
η2)]/[10νL2{2I(2I - 1)}2], δQ4(θ,φ) · P4(cos β) describes the
quadrupolar line shape, νL is the Larmor frequency, and 〈δ1〉 is
the first moment of the quadrupolar line shape in the first
dimension. More information and a more general derivation for
all half-integer quadrupolar spins are presented in the Supporting
Information.
All data were processed with the program RMN.48 Single
field 1D spectra were simulated with the program DMFIT.49
Simulations of the multiple field static echo patterns and
difference spectra from the incomplete DFS experiments were
achieved by using an iterative fitting method with the program
WSOLIDS.50 Errors for the NMR parameters determined with
the WSOLIDS programs were estimated based both on visual
inspection and on the change in the parameter that yielded a
doubling in the sum of the squares of the deviation of the
observed data from the model.
4. Ab Initio Calculations. The first-principle periodic cal-
culations were carried out utilizing DFT with a generalized
Burke, and Ernzerhof51 as implemented in the WIEN2k code.52
The electrons of the atoms were considered without any core
approximation. Full potential (linearized) augmented plane
waves plus local orbitals (L/APW+lo)53,54 were used. Better
convergence was ensured with a combination of basis functions,
with s and p states in LAPW mode and the d state in APW+lo
mode. The core states were treated fully relativistically and for
the valence states a scalar, relativistic scheme was employed
with -6.0 Ry as the cutoff energy. Temperature smearing of
0.002 Ry was used throughout the calculation to help in the
elimination of virtual states emerging from the possible non-
linearization of the wave functions. The charge density mixing
scheme used was the multisecant method55 with 0.1 as the
mixing parameter. All calculations were performed in single
processor mode with the Clark University Computing Cluster,
which is comprised of two integrated Linux clusters with 48
dual processor nodes.
The muffin-tin radii used were Rmt(Nb) ) 1.7 au, Rmt(O) )
1.3 au, Rmt(Rb) ) 2.4 au, Rmt(Sr) ) 2.2 au, and Rmt(H) )
0.99 au. The number of plane waves describing the system is
defined by a cutoff parameter RmtKmax, where Rmt (muffin-tin
radius) is the minimum radius of all the atoms present and Kmax
is the largest K vector in the plane wave expansion. To ensure
proper convergence, calculations up to RmtKmax ) 7.00 for the
rubidium form and up to RmtKmax ) 5.00 for the acid-exchanged
form were carried out and showed no appreciable changes in
the observed quantities compared to those determined with
RmtKmax ) 6.50 or 6.00 for the rubidium form and with RmtKmax
) 4.50 or 4.00 for the acid-exchanged form. The cutoff of
Distortions of the Dion-Jacobson Phase RbSr2Nb3O10
Figure 2. X-ray powder diffraction patterns for RbSr2Nb3O10 (top)
and HSr2Nb3O10. (bottom). Possible impurity reflections are designated
by asterisks.
TABLE 1: Lattice Constants for the Rubidium and
Acid-Exchanged Formsa
a (Å) c (Å)
Rb form P4/mmm 3.8988(1) 15.2831(5)
P4/mbm 5.5136(1) 15.2834(5)
Pbamb 5.5127(4) 15.2835(5)
5.5148(5)
H form P4/mbm 5.5077(3) 14.8357(18)
Pbamb 5.5057(18) 14.8437(28)
5.5093(19)
a
Error on the last digit(s) is listed in parentheses. b For the
orthorhombic space group, the b lattice constant is listed below the
a lattice constant.
charge density expansion in the interstitial region is limited to
Gmax ) 12 (20 for the acid-exchanged form). For full conver-
gence in terms of the irreducible wedge of the Brillouin zone
(IBZ), the sampling was done up to 15 special k-points, which
corresponds to a 9 × 9 × 3 Monkhorst-Pack mesh56 in the
full Brillouin zone. Higher k-point sampling did not alter the
results significantly showing the acceptable achievement of the
saturation point. For the relaxation of the structures, RmtKmax )
5.00 was used with 10 k-points in the IBZ. The NEW1
minimization method was used, and a calculation with final
forces less than 5 mRy/au was considered relaxed.
The EFG tensor was determined from the expansion of the
converged self-consistent electron density over the spherical
harmonics of the wave. The periodic calculation takes into
account the representative unit cell with infinite repetition in
all three dimensions. As the calculation is self-consistent and
deals with all electrons, no Sternheimer shielding factor was
needed. The quadrupolar moments used for 87Rb and 93Nb were
13.35 and -32.0 fm2, respectively.57 While the sign of the VZZ
component could be determined in the calculation, it was ignored
as NMR is not sensitive to the sign.
Results
1. X-ray Powder Diffraction. The powder diffraction data
(Figure 2) for the rubidium sample and the acid-exchanged form
were analyzed by using LeBail fits to determine the lattice
parameters. The parameters derived from the fits with use of a
P4/mmm space group are listed in Table 1. The lattice
parameters for the rubidium form match the literature values.23
A small impurity phase was observed in the diffraction pattern
J. Phys. Chem. C, Vol. 113, No. 40, 2009 17551
Figure 3. 87Rb MAS one-pulse NMR spectrum (top) and simulated
spectrum (bottom), using the parameters listed in Table 2.
but was not clearly identified. The values for the acid-exchange
form show the expected decrease in the c axis as the space
between layers decreases due to the smaller cation. The decrease
of 0.44 Å is similar to the change observed in other
Dion-Jacobson materials upon acid exchange.58 The lateral
dimensions of the layers do not appear to change as the a axis
length is the same for the acid-exchanged form.
The unit cell described by the literature represents the smallest
unit cell possible for the triple-layer perovskites. A unit cell with
double the volume is also a possible structure. The lattice constants
for the a axis differ by the square root of two, which is achievable
if the doubled structure has octahedra at both the corner and the
center of the ab plane. The space groups P4/mbm, P4jb2, P4bm,
and P4/m will accommodate such a structure. The increased size
of the unit cell allows for tilting of the octahedra, which can
lengthen the Nb-O bonds (vide infra). Lower symmetry space
groups with an expanded unit cell such as Pbam were also fit
by using the LeBail approach. The values for the lattice constants
are reported in Table 1.
2. Solid State NMR. 87Rb MAS experiments yielded a well-
defined quadrupolar powder pattern that could be fit by using
one rubidium environment (Figure 3). The isotropic chemical
shift for the site was -4.1 ( 0.1 ppm, the value of CQ was 5.1
( 0.1 MHz, and the value of η was 0.04 ( 0.01 (Table 2). The
sharp features of the signal allude to a well-organized sample
that most likely has only one crystallographic site for the
rubidium cation.
93
Nb MAS spectra were not well-defined due to the large
sideband pattern as the maximum spinning rate was not
sufficient to average the different anisotropies. However, rotor
synchronized MQMAS was able to resolve the different 93Nb
environments of low to moderate quadrupolar couplings due to
the shearing method applied (Figure 4). Different environments
with very different quadrupolar couplings can be clearly
observed due to the different locations of the powder patterns
along the anisotropic axis. The more the powder pattern is
shifted to larger negative values, the larger the value of CQ.
The separation of the line shapes along with the alignment of
the sidebands makes the determination of CQ, η, and the
isotropic chemical shift possible even with experiments in which
the MAS rate is not large enough to minimize the presence of
sidebands. The extent of the sideband pattern along the isotropic
dimension also gives an indication of the size of the static
powder pattern for the particular site and thus an indication if
the site has a large CSA in addition to quadrupolar anisotropy.
Due to incomplete excitation of the total sideband manifold,
the intensities of all the sidebands for the broad patterns are
not reproduced properly, hence the discrepancies between the
summed spectra and the simulated spectra. However, using the
17552 J. Phys. Chem. C, Vol. 113, No. 40, 2009 Wang et al.

TABLE 2: NMR Fit Parametersa

δISO (ppm) CQ (MHz) η Ω (ppm) κ Rb (deg) β (deg) γb (deg)
RbSr2Nb3O10
Rb -4.1(1) 5.1(1) 0.04(1)
Nb1 -1060(9) 93.0(4) 0.01(2) 530(30) 0.80(11) 0(80) 1(1) 0(80)
Nb2 -971(9) 44.6(6) 0.05(3) 820(25) 0.85(6) u 0(1) u
Nbi -1008(15) 29.5(6) 0.09(6) 120(35) -0.6(3) 80(10) 75(15) 70(20)
HSr2Nb3O10
Nb1 -1069(11) 86.0(9) 0.02(2) 540(30) 0.66(10) 0(30) 1(2) 0(30)
Nb2 -1148(9) 38.5(5) 0.06(3) 560(25) 0.75(11) u 0(1) u
a
Error on the last digit(s) is listed in parentheses. b Angle undefined (u) if β ) 0.

Figure 4. 93Nb triple quantum MQMAS 2D spectrum of RbSr2Nb3O10 with alternate shearing scheme (left); sum spectrum of side bands (black
line) for different sites with the accompanying simulation (red line) based on parameters listed in Table 2 (right). The two sum spectra are offset
from each other due to different sizes of the EFG tensors. The origins of the different sum spectra are linked to the final spectrum via the black
arrows.

Figure 5. 93Nb triple quantum MQMAS 2D spectrum of HSr2Nb3O10 with alternate shearing scheme (left); sum spectrum of side bands (black
line) with the accompanying simulation (red line) based on parameters listed in Table 2 (right). No small EFG site was observed with the acid-
exchanged form.

position of the singularities in the powder pattern, the values
for CQ and η can be determined. In addition, only CQ and η for
the site control the effective isotropic shift for the powder pattern
along the anisotropic axis and serve as an additional measure
of the size of the anisotropy (see the Supporting Information
for more details).
For the rubidium form, two environments of different CQ
values are clearly distinguished (Figure 4). From the location
of the singularities for the larger CQ environment and the pattern
for the smaller CQ environment (referred to as Nb2 and Nbi),
the CQ values were extracted yielding 44.6 and 29.5 MHz and
asymmetry parameters of 0.05 and 0.09, respectively. To better
distinguish the more negative singularity for the large CQ
environment, a second MQMAS experiment was conducted with
a shift in the transmitter offset to better excite the region on the
more negative side of the sideband envelope. The improved
intensity of the sideband pattern on this side confirmed the
location of the singularity, further justifying the EFG values
assigned for this environment (Supporting Information, Figure
S1). It appears that the environment with the larger EFG
anisotropy also has a significant CSA as such an EFG alone
would only have a sideband manifold of approximately 1500
ppm. The values associated with the two environments are listed
in Table 2.
The MQMAS experiment on the acid-exchanged form only
showed one environment in the low to moderate EFG range
(Figure 5). The singularities in the powder pattern had better
intensities, as the sideband manifold was not as extensive as in
the Rb form due to the smaller EFG and a smaller CSA. The
environment had a CQ value of 38.5 MHz and an asymmetry
parameter of 0.07. The values for this environment are listed
in Table 2.
To determine the CSA and the relative populations for the
various niobium environments, since MQMAS is not inherently
Distortions of the Dion-Jacobson Phase RbSr2Nb3O10 J. Phys. Chem. C, Vol. 113, No. 40, 2009 17553

Figure 6. 93Nb static VOCS spectra for RbSr2Nb3O10 at 9.4 (a) and 14.1 T (b). The original spectra are shown at teh top and the final simulations
using the parameters listed in Table 2 are shown second from the top. The bottom three simulated spectra, in order from top to bottom, are for the
external site, Nb2, the interior site, Nb1, and the impurity, Nbi, using the parameters from Table 2.

Figure 7. 93Nb static VOCS spectra for HSr2Nb3O10 at 9.4 (a) and 14.1 T (b). The original spectra are shown at the top and the final simulations
using the parameters listed in Table 2 are shown second from the top. The bottom two simulated spectra, in order from top to bottom, are for the
external site, Nb2, and the interior site, Nb1, using the parameters from Table 2.

quantitative, wide-line experiments were conducted with use
of the VOCS method to extend the frequency range covered
by the experiment (Figures 6 and 7). Initial experiments revealed
the static powder patterns for the environments observed in the
MQMAS experiments. When the frequency offsets were
expanded such that the window covered was (600 kHz, it
became clear that an additional niobium environment (Nb1) was
present with a significantly larger EFG and CSA. While some
reduction in the width was observed with the acid-exchanged
form, the large EFG environment was present in both samples.
The lower population of this more anisotropic environment also
contributed to the initial difficulty in its detection. Using the
two magnetic fields, the EFG and CSA for the two major
niobium environments were determined. In both the rubidium
and acid-exchanged forms, the ratio of the larger EFG to the
smaller EFG environment was 1:2, which matches the ratio of
interior sites to exterior sites found in the crystallographic
structure for triple-layer perovskites (Figure 1).
The larger EFG environments (Nb1) had CQ values of 93
MHz for the rubidium form and 86 MHz for the acid-exchanged
form, which explains why these environments were not observed
in the MQMAS experiments. Both environments had asymmetry
parameters of nearly zero. The CSA for the larger EFG
environments were similar with spans of 530-540 ppm and
skews that were nearly similar with values of 0.8 and 0.7 for
the rubidium and acid-exchanged forms, respectively. The tensor
values for the EFG and CSA for the environments are listed in
Table 2. For both samples, the EFG tensors are effectively
axially symmetric. However, the CSA tensors for both samples
do not have this symmetry. The EFG and CSA tensors are
aligned in both samples for the large EFG environments.
For the smaller EFG environments in the two samples, the
values for the CSA tensors and the angles between the EFG
and CSA tensors were determined by using the multiple field
data; the EFG tensor values were set according to the MQMAS
results. For this environment in the rubidium form, the CSA
was found to be significantly larger with a span of 820 ppm
and a skew of 0.85. In the acid-exchanged form, the CSA tensor
was similar to that for the larger EFG environment with a span
of 560 ppm and a skew of 0.75. For both samples, the primary
axes of both tensors were aligned, as β is effectively zero. The
values for the simulations are listed in Table 2.
The smallest EFG environment (Nbi) is probably due to an
impurity in the sample. While it was observed in the MQMAS
17554 J. Phys. Chem. C, Vol. 113, No. 40, 2009 Wang et al.

Figure 8. 93Nb difference spectra for RbSr2Nb3O10 created from incomplete DFS experiments at 9.4 (a) and 14.1 T (b) are shown at the top.
Converging frequency sweeps from 650 to 250 kHz were used. The simulated spectra shown at the bottom use the parameters for the impurity, Nbi,
listed in Table 2. An artifact from the external site, Nb2, is observed at the more negative frequencies and was not included in the simulation.

experiment on the rubidium sample, it is difficult to observe in

the wide-line spectra and could not be properly simulated by
using the two-field data collected. To properly describe the two
sites, it is necessary to determine the contribution of the impurity
to the overall powder pattern. To resolve this environment,
incomplete DFS experiments44 were conducted at both 9.4 and
14.1 T (Supporting Information, Figure S2) and the difference
spectra were used to resolve the contribution from this third
niobium environment (Figure 8). Since the effectiveness of the
technique is dependent on the inherent difference in the width
of the satellite transition patterns of the different niobium
environments, some excitation of the other environments is
possible. However, the values from the MQMAS experiment
can help determine the appropriate start frequency, and the
sideband pattern observed indicates that the extent of the static Figure 9. {1H}-93Nb cross-polarization spectrum for HSr2Nb3O10
powder pattern should be around 300 ppm or less based on the recorded at 9.4 T (top) and the simulated spectra (bottom) using the
parameters for the exterior site, Nb2, listed in Table 2.
MAS rate of 28.5 kHz. An isolated line shape was found for
the difference spectra at both magnetic fields that corresponded TABLE 3: DFT Calculation Results for RbSr2Nb3O10
with the isotropic chemical shift determined through MQMAS.
CQ (MHz) η
Due to the selection of the start and final frequencies for the
sweep, a small part of the line shape for the other smaller EFG Nb1 Nb2 Rb Nb1 Nb2 Rb
environment was also enhanced. The fragment from the Nb2 literature structure -21.057 37.174 3.033 0.00 0.00 0.00
site corresponds to the edge of the powder pattern (as seen in (P4/mmm)
the original DFS spectrum in Figure S2 in the Supporting relaxed structure -3.314 9.773 5.823 0.00 0.00 0.00
Information) and thus was not included in the simulated powder (P4/mmm)
proposed structure -93.499 44.529 5.206 0.00 0.00 0.01
pattern for the impurity. With the two-field data, the CSA tensor (P4/mbm)
information was found through simulation although the param-
eters are less accurate due to the lack of significant resolvable
features. The values for the simulation of this environment are the rubidium site in the structure. The structure based on the
listed in Table 2. The incorporation of this environment into literature yielded results that were radically different from the
the wide-line simulation of the rubidium form accounted for observed experimental NMR values (Table 3). Often better
the lack of the deep valley expected in the axially symmetric agreement between theory and experiment has been achieved
powder patterns and explained the presence of a narrow valley through relaxation of the crystallographic structure. Relaxation
in the 14.1 T wide-line spectrum. of the atom positions for the P4/mmm structure did not yield a
While the assignment of the smaller EFG environment to the significant improvement for the values of the EFG for the
exterior niobium site would be appropriate based on the relative niobium sites but did bring the rubidium site EFG closer to the
populations of the large and small EFG environments, CP experimental values.
experiments were conducted to further determine which niobium With the failure of the P4/mmm structure to match the
environment was in close proximity to the proton in the acid- experimental NMR data, alternate structures were explored to
exchanged form. The static CP experiment further confirms the find an improved match with experimental values. The use of
assignment that the smaller EFG site is associated with the a P4/mbm structure afforded the opportunity to vary the Nb-O
proton as it was the only pattern that had polarization transfer bond lengths for the interior site in particular. The lower
(Figure 9). Furthermore, the pattern that was observed does symmetry space group permits the tilting of the octahedra with
match the shape of the powder pattern simulated by using the the rotation axis parallel to the c axis. The lack of a structure
data derived from the MQMAS and VOCS experiments. necessitated that the values of the tilt angle be varied to search
3. Ab Initio Calculations. The literature structure of the for a value of |VZZ| that was in the vicinity of the experimental
rubidium form23 was used in DFT calculations to determine the values. The change in tilt angle for the interior site generally
CQ and η values for the two crystallographic niobium sites and had only a small effect on the size of the VZZ value for the
Distortions of the Dion-Jacobson Phase RbSr2Nb3O10
Figure 10. Plot of the quadrupolar coupling of the interior site (Nb1)
and the exterior site (Nb2) niobium atoms in RbSr2Nb3O10 versus the
tilt angle of the interior octahedron is shown at the bottom. A fit (black
line) of the interior site CQ values using eq 4 is included. The fit
equation, with error in parentheses, was -663(11) + 625(12) cos3 θ.
The nature of the rotation (yellow arrow) is shown with the depiction
of the interior site (niobium, green; oxygen, red; strontium, blue) at
the top.
Figure 11. Plot of the quadrupolar coupling of the interior site (Nb1)
and the exterior site (Nb2) niobium atoms in RbSr2Nb3O10 versus the
tilt angle of the exterior octahedron is shown at the bottom. A fit (black
line) of the exterior site CQ values using eq 4 is included. The fit
equation, with error in parentheses, was -465(7) + 512(7) cos3 θ. The
nature of the rotation (yellow arrow) is shown with the depiction of
the exterior site (niobium, green; oxygen, red) at the top.
exterior site, and vice versa (Figures 10 and 11). Thus the tilt
angles could be optimized independently. The observed CQ for
the rubidium site was sensitive to the terminal Nb-O bond
length of the exterior site and served as an additional constraint
for the modification of the structure used in the calculations. A
Rb-O bond length of 3.13 Å for the eight Rb-O bonds yielded
an appropriate CQ value for the rubidium site. A potential
J. Phys. Chem. C, Vol. 113, No. 40, 2009 17555
Figure 12. Plot of the total energy calculated with WIEN2k for the
RbSr2Nb3O10 structure versus the tilt angle of the interior site (Nb1)
octahedron.
Figure 13. Plot of the total energy calculated with WIEN2k for the
RbSr2Nb3O10 structure versus the tilt angle of the exterior site (Nb2)
octahedron.
structure was found that matched the experimental values found
with 93Nb NMR (Table 3). The total energies for the different
structures were calculated and are plotted as a function of tilt
angle (Figures 12 and 13). For both sites, the lowest energy
structure correlates well with the structures that are closest to
the observed EFG values. In the case of the exterior site, a sign
relative to the tilt direction of the interior site could be established.
The tilt angle for the two niobium sites were 14((1)° and -3((1)°
for the interior and exterior sites, respectively. The axial bond length
for the interior site was 1.95 Å. The axial bond lengths for the
exterior site were 1.75 Å for the terminal bond and 2.45 Å for the
bridging oxygen.
The utility of the DFT calculations is limited for the acid-
exchanged material (HSr2Nb3O10) without a clear structure with
a known hydrogen atom position. Difficulties associated with
the appearance of spurious eigenvalues, or ghost bands, limited
the possible structures as an Rmt of the hydrogen atom could
not be made small enough to create short O-H bonds. A
structure with a P1 space group was used to facilitate the
placement of the hydrogen atom at different positions between
the layers. Starting with the structure derived for the rubidium
form, the change in the interlayer spacing was introduced while
the bond distances within the layers were maintained. To attempt
to match the observed CQ values, the lengths of the axial Nb-O
bonds were varied (Table 4). Calculations were run for structures
that had the hydrogen atom equally shared by the layers through
hydrogen bonding and that had the hydrogen more tightly held
by one of the terminal oxygen atoms. The lower symmetry space
group and different relative positions for the hydrogen atoms
17556 J. Phys. Chem. C, Vol. 113, No. 40, 2009 Wang et al.

TABLE 4: Effect on the Electric Field Gradient and Quadrupolar Coupling of Nb upon Variation in the Nb1-O2 (bridging
O-atom) Bond Length in HSr2Nb3O10a
Nb1 Nb2a Nb2b
Nb1-O2 bond length (Å) EFG (1021 V/m2) CQ (MHz) EFG (1021 V/m2) CQ (MHz) EFG (1021 V/m2) CQ (MHz)
1.938 -13.806 -106.821 4.212 32.596 4.363 33.762
1.945 -12.869 -99.575 4.070 31.496 4.248 32.874
1.952 -12.007 -92.906 3.928 30.400 4.132 31.975
1.960 -11.092 -85.827 3.776 29.215 4.008 31.009
1.967 -10.309 -79.765 3.640 28.162 3.896 30.149
a
P1 space group with the same tilt angle Nb1-O-Nb1 as in the parent compound RbSr2Nb3O10.

TABLE 5: Effect on the Electric Field Gradient of the

External Site upon Variation in the Differences of the of 4/mmm. The P4/mbm structure can account for the nonaxial
Terminal O-H Bond in HSr2Nb3O10a symmetry of the atom, as it would be located at a 2c position
with site symmetry of mmm. The translation to the P4/mbm
Nb2a Nb2b
(long O-H bond)b (short O-H bond)b
structure would also maintain the restriction of one crystal-
lographic rubidium atom in the asymmetric unit, which appears
difference in O-H EFG CQ EFG CQ to be the case in the 87Rb MAS spectrum (Figure 2). The
bond lengths (Å) (1021 V/m2) (MHz) (1021 V/m2) (MHz)
possibility of the structure corresponding to the P4/mbm space
0.352 3.029 23.436 4.430 34.274 group has been suggested based on Raman spectroscopy.25
0.246 3.338 25.828 4.300 33.269
0.166 3.565 27.583 4.169 32.261
From the 93Nb NMR, it is clear that the local site symmetry
0.086 3.776 29.215 4.008 31.009 for the niobium positions in the rubidium form does not contain
a 4-fold axis. The exterior site clearly has a nonaxial EFG tensor
a
P1 space group with Nb1-O ) 1.960 Å, Nb2a-O ) 1.755 Å, while the asymmetry parameter for the interior niobium site is
and Nb2b-O )1.762 Å. b (Nb2a) O-H ) 1.599 Å and (Nb2b)
O-H ) 1.247 Å for the first set of calculations.
zero within the error. However, the CSA tensors for both sites
clearly point to a nonaxial tensor environment. As with the
TABLE 6: Effect on the Electric Field Gradient of External position of the rubidium atom, this would eliminate the
Site upon Variation in the Differences of the Terminal O-H possibility of the niobium atoms sitting at positions with 4-fold
Bond in HSr2Nb3O10 When the Terminal Bond Is Longera symmetry and thus prevent the structure from being described
Nb2a Nb2b by any tetragonal space group. Nevertheless, the actual structure
(long O-H bond)b (short O-H bond)b would not deviate extremely from the tetragonal structure as
difference in O-H EFG CQ EFG CQ the near-axial nature of the tensors attests to the similarity to
bond lengths (Å) (1021 V/m2) (MHz) (1021 V/m2) (MHz) the idealized higher symmetry structure. As the Euler angle β
is essentially zero, the alignment of the EFG and CSA tensors
0.305 4.631 35.833 4.176 32.311
0.199 4.770 36.909 4.071 31.503 for both environments further points to the relatively high
0.119 5.292 40.946 4.067 31.471 symmetry nature of the structure that is present. A lower
0.039 5.362 41.485 3.683 28.495 symmetry group along the lines of Pbam or Pba2 would satisfy
the symmetry requirements for both the rubidium and niobium
a
P1 space group with Nb1-O ) 1.960 Å, Nb2a-O ) 1.806 Å,
and Nb2b-O )1.762 Å. b (Nb2a) O-H ) 1.552 Å and (Nb2b) sites.
O-H ) 1.247 Å for the first set of calculations. It is interesting to note that the size of the EFG tensor values
for the two sites is not necessarily what would be expected based
on the appearance of the niobium sites. In particular, the interior
effectively split the exterior sites and are referred to as Nb2a niobium site would appear to be relatively symmetric, yet the CQ
and Nb2b. The results of the various structures are shown in value is one of the largest recorded for 93Nb.36 The conventional
Tables 5 and 6. expectation has been that the EFG would increase as the
octahedral site became increasingly rhombic;60 yet the interior
Discussion site does not drastically deviate from tetragonal symmetry. It
Since the utility of X-ray powder diffraction methods for is clear that the long-range lattice with the influence of the
crystal structure solutions is limited due to the overlapping of positively charged alkaline earth cations, along with the oxygen
reflections, additional information from NMR experiments is atoms further out, add to the EFG, although in this case, the
necessary to constrain the list of possible structures. The simple effect of the increase in bond length caused by the tilt
crystallographic symmetry of the structure can place restrictions of the octahedra plays an even greater role in determining the
on the symmetry of the NMR tensor for that site. The local magnitude of the gradient. Symmetry in these materials does
symmetry established by the space group can limit the directions not imply an effective cancellation or reduction of the gradient.
of the tensor components and their relative magnitudes, es- The DFT calculations further support the presence of a tilt
sentially dictating whether or not axial symmetry must be in the octahedra and the resulting deviation from P4/mmm
present.59 From the EFG and CSA tensors for the two quadru- symmetry. The calculated EFG values for the literature structure
polar nuclei in the samples, it is possible to determine if the are in line with the expectation that the high symmetry interior
proposed structures are appropriate. The 87Rb NMR yields an site would have a small EFG. As no nearly isotropic EFG
EFG tensor with nonaxial symmetry as η ) 0.04. In this case, environments were observed experimentally, the structural
the rubidium atom cannot be located at a position with site model used was clearly not appropriate. Since previous Raman
symmetry higher than orthorhombic. This constraint thus studies have alluded to a tilt in the octahedra, the P4/mbm
invalidates the P4/mmm structure for the rubidium form as the structure with an expanded unit cell was utilized in order to
rubidium atom would sit at the 1d position with site symmetry obtain the flexibility needed in the calculations to vary the EFG
Distortions of the Dion-Jacobson Phase RbSr2Nb3O10
at the two sites. The adjustments in the oxygen atom positions
were further controlled by the need to match the 87Rb EFG
values. The primary modification was in the tilt of the octahedra
as the assumption was that the laboratory powder X-ray
diffraction data were unable to determine the small shift in the
ab plane that created the tilt. The modification resulted in a
structure that better matched the NMR results.
The tilt of the interior niobium site had a drastic effect on
the size of the EFG making possible the determination of the
size of the tilt (Figure 10). A tilt of 14° yields a CQ value within
the error of the experimentally determined value and is
consistent with the magnitude of the tilt angles found in other
perovskites.24,61 The exterior site seemed to have a smaller tilt
angle (Figure 11) and its orientation relative to the interior site
could only be determined based on the total calculated energy
(Figure 13). The coordination of the strontium atoms would
appear to perturb the orientation of the octahedra. A tilt of the
interior site octahedra brings two of the four equatorial oxygen
atoms into closer proximity with the strontium atom with a
change to 2.66 Å from the original distance of 2.96 Å. A slight
tilt of the exterior site octahedra would result in two oxygen
atoms moving even closer to the strontium atom. Without the
tilt at the exterior site, the strontium cation has six oxygen atoms
at a close distance of approximately 2.66 Å. These oxygen atoms
lie closer than the axial oxygen atoms at the interior site, which
sit at a distance of 2.77 Å from the strontium. The improved
coordination would explain why significant tilting only occurs
at the interior site.
The value of CQ for both sites appears to have a similar
dependence on the tilt angle. A simple point charge model of
an octahedron in which the change in the equatorial Nb-O bond
length depends on the tilt angle predicts a cos3 θ dependence:
[ ]
2e2Q 2Zax 2Zeq
CQ ∝ - 3 cos3 θt (4)
h 3
rax req,0
where Z is the charge for the axial and equatorial oxygen atoms,
rax is the axial Nb-O bond length, req,0 is the equatorial Nb-O
bond length if no tilt was present, and θt is the tilt angle. Both
data sets follow this functional form reasonably well (Figures
10 and 11). The influence of the lattice outside the octahedron
should have an effect on the final values but this is most likely
manifested as an offset for the function. The coefficients for
both terms are different for the two sites. As the sites have
different charged cations in close proximity, it is not surprising
that the offset differs. However, the change in the coefficient
for the cosine term can be explained by the change in the
geometry of the octahedron. If a non-90° bond angle is allowed
for the equatorial oxygen atoms, then the influence on the Nb-O
bond length can be introduced. The modified point charge model
equation is now:
2e2Q
CQ ∝ × candidate would be an increase in the O-Nb-O bond angle
h
[ ]
Zax1 Zax2 2Zeq(3 cos2 θONbO - 1)sin3 θONbO 3
+ + cos θt
r3ax1 r3ax2 3
req,0
(5)
where rax1 and rax2 are the short and long axial Nb-O bond
lengths and θONbO is the bond angle between axial and equatorial
oxygen atoms. When the O-Nb-O angle is greater than 90°,
J. Phys. Chem. C, Vol. 113, No. 40, 2009 17557
the coefficient will become smaller. For the bond angle of 100.9°
used in the DFT calculations at the exterior site in the structure,
the coefficient is predicted to decrease by a factor of 0.85. The
observed ratio between the coefficients derived from the DFT
based data is 0.82 ( 0.02. A bond angle of 101.8° would give
this ratio. While the point charge model is not exact in describing
the differences observed in the structure, it is clear that it can
serve as a reasonable qualitative model for trends in these
Dion-Jacobson niobates and possibly other niobates.
The acid exchange of the material produced changes at both
niobium sites implying that protonation does not only affect
the structure of the surface site. Both sites have a decrease in
CQ value of approximately 7 MHz but very little change in
symmetry is observed. Changes related to the isotropic chemical
shift and the CSA are limited to the exterior site only.
Protonation of the terminal oxygen atom results in a change in
the isotropic chemical shift of 177 ppm and a decrease in the
span of the CSA of 260 ppm as observed from both the static
echo and static CP experiments. The bonding of the proton with
the terminal oxygen atom would be expected to change its
bonding with the niobium atom. The lack of change in symmetry
implies that the effect is mostly limited to the change in the
length of the terminal Nb-O bond or at least a change in the
niobium atom position along the c axis relative to the oxygen
atoms in the polyhedron. The net effect must reduce the
asymmetry of the polyhedron to account for the reduction in
both anisotropic interactions.
The DFT calculations help to clarify the possible changes in
the structure that might occur upon protonation. The variations
in the bond length of the axial Nb-O bond of the interior site
show that a small change in length can drastically affect the
EFG at the interior site when the same tilt angle as in the
rubidium form is used (Table 4). A change of 7 MHz could
easily be achieved by a simple increase of approximately
0.01 Å. The change in the position of this bridging oxygen
significantly alters the EFG at the exterior by 1-2 MHz. So
the rearrangement of the bridging oxygen atoms can explain
some of the decrease at the exterior site, but some changes
involving the other oxygen atoms of the site must occur.
The various models with hydrogen atoms being equally shared
across the gap or preferentially bound to one oxygen atom
demonstrate the effect of the increasing strength of the O-H
bond on the niobium EFG (Table 5). A tightly held hydrogen
atom increases the magnitude of the EFG and a longer O-H
bond decreases it. A difference in O-H bond length of 0.35 Å
leads to a difference of 11 MHz in CQ. Similarly, the longer
the terminal Nb-O bond, the larger the size of the EFG. A
change in the bond length of 0.051 Å increased the CQ value
by 12 MHz if the oxygen is not bonded to hydrogen as seen in
the change for the Nb2a site. As the expectation is that the
terminal Nb-O bond should increase in length upon protonation
due to loss in electron density in the bond, additional rearrange-
ments must occur that lead to the net decrease in the EFG. One
resulting in the niobium atom sitting further away from the
equatorial oxygen atoms. On the basis of the calculations on
the rubidium form, the increase in the O-Nb-O bond angle
will decrease the size of the EFG. In a sense, an elongation of
the five-coordinate polyhedron would occur with the protonation.
Without further information to constrain the structure, such as
17
O EFG information, it is not possible to conclusively determine
the changes responsible for the decrease in the EFG at the
exterior site, although it is clear that some combination of
17558 J. Phys. Chem. C, Vol. 113, No. 40, 2009
increase in bond length and bond angle must be responsible
for the observed change in 93Nb EFG values.
Conclusion
Solid-state NMR and DFT methods were able to clarify the
structure of RbSr2Nb3O10 and elucidate the structural changes
that must occur upon acid exchange of this compound. 93Nb
MQMAS and multiple field VOCS-based wide-line NMR
experiments were able to determine the EFG and CSA tensor
information for the different niobium environments in a triple-
perovskite layered niobate. The spectra demonstrate that the
niobium site symmetry is lower than what is expected based
on the known literature structure and that octahedral tilting must
be present. Periodic all-electron DFT calculations were capable
of reproducing the EFG values observed if tilting is incorporated
into the structure. The tilting does not significantly distort the
structure from a tetragonal lattice and occurs along only one
direction. The magnitude and direction of the rotation differs
for the two niobium sites with the interior site having a larger
deviation of 14° and the exterior site having a tilt of -3°. Acid
exchange of the interlayer cation resulted in changes in the
structure for both sites. DFT calculations of the trends associated
with different Nb-O bond lengths point to only a change in
axial bond lengths for the interior site. However, changes in
the exterior site must be more complex with changes associated
with not only the axial Nb-O bonds but also the bond angles
associated with the equatorial oxygen atoms. The use of 93Nb
NMR in conjunction with quantum mechanical calculations can
yield insights on the subtle changes in structure that occur with
postsynthetic processing and could prove to be useful for the
study of these layered niobates under conditions of exfoliation
or restacking when X-ray diffraction may not be informative.
Acknowledgment. The work was supported in part by the
Petroleum Research Fund (PRF 46923-AC5) and NSF Grant
No. DMR-0748399. The computer cluster work was supported
in part by NSF Grant No. DBI-0320875. The X-ray powder
diffraction equipment was supported by the Kresge Foundation
Science Initiative.
Supporting Information Available: Derivation of alternate
shearing scheme, 93Nb MQMAS spectrum for offset experiment,
additional DFS spectra, listing of EFG values, and crystal
structures used for WIEN2k calculations. This material is
available free of charge via the Internet at http://pubs.acs.org.
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