ArticlePDF Available

Abstract and Figures

We report magnetic and thermodynamic properties of a $4d^1$ (Mo$^{5+}$) magnetic insulator MoOPO$_4$ single crystal, which realizes a $J_1$-$J_2$ Heisenberg spin-$1/2$ model on a stacked square lattice. The specific-heat measurements show a magnetic transition at 16 K which is also confirmed by magnetic susceptibility, ESR, and neutron diffraction measurements. Magnetic entropy deduced from the specific heat corresponds to a two-level degree of freedom per Mo$^{5+}$ ion, and the effective moment from the susceptibility corresponds to the spin-only value. Using {\it ab initio} quantum chemistry calculations we demonstrate that the Mo$^{5+}$ ion hosts a purely spin-$1/2$ magnetic moment, indicating negligible effects of spin-orbit interaction. The quenched orbital moments originate from the large displacement of Mo ions inside the MoO$_6$ octahedra along the apical direction. The ground state is shown by neutron diffraction to support a collinear N\'eel-type magnetic order, and a spin-flop transition is observed around an applied magnetic field of 3.5 T. The magnetic phase diagram is reproduced by a mean-field calculation assuming a small easy-axis anisotropy in the exchange interactions. Our results suggest $4d$ molybdates as an alternative playground to search for model quantum magnets.
Content may be subject to copyright.
PHYSICAL REVIEW B 96,024445 (2017)
J1-J2square lattice antiferromagnetism in the orbitally quenched insulator MoOPO4
L. Yang,1,2M. Jeong,1,*P. Babk e v i ch, 1V. M . K a tu ku r i , 3B. Náfrádi,2N. E. Shaik,1A. Magrez,4H. Berger,4J. Schefer,5
E. Ressouche,6M. Kriener,7I. Živkovi ´
c,1O. V. Yazyev,3L. Forró,2and H. M. Rønnow1,7,
1Laboratory for Quantum Magnetism, Institute of Physics, Ecole Polytechnique Féderale de Lausanne, CH-1015 Lausanne, Switzerland
2Laboratory of Physics of Complex Matter, Institute of Physics, Ecole Polytechnique Féderale de Lausanne, CH-1015 Lausanne, Switzerland
3Chair of Computational Condensed Matter Physics, Institute of Physics, Ecole Polytechnique Féderale de Lausanne,
CH-1015 Lausanne, Switzerland
4Crystal Growth Facility, Institute of Physics, Ecole Polytechnique Féderale de Lausanne, CH-1015 Lausanne, Switzerland
5Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, CH-5232 Villigen, Switzerland
6Université Grenoble Alpes, CEA, INAC, MEM, F-38000 Grenoble, France
7RIKEN Center for Emergent Matter Science, Wako, Saitama 351-0198, Japan
(Received 17 May 2017; published 28 July 2017)
We report magnetic and thermodynamic properties of a 4d1(Mo5+) magnetic insulator MoOPO4single crystal,
which realizes a J1-J2Heisenberg spin-1/2 model on a stacked square lattice. The specific-heat measurements
show a magnetic transition at 16 K which is also confirmed by magnetic susceptibility, ESR, and neutron
diffraction measurements. Magnetic entropy deduced from the specific heat corresponds to a two-level degree of
freedom per Mo5+ion, and the effective moment from the susceptibility corresponds to the spin-only value. Using
ab initio quantum chemistry calculations, we demonstrate that the Mo5+ion hosts a purely spin-1/2 magnetic
moment, indicating negligible effects of spin-orbit interaction. The quenched orbital moments originate from the
large displacement of Mo ions inside the MoO6octahedra along the apical direction. The ground state is shown
by neutron diffraction to support a collinear Néel-type magnetic order, and a spin-flop transition is observed
around an applied magnetic field of 3 .5 T. The magnetic phase diagram is reproduced by a mean-field calculation
assuming a small easy-axis anisotropy in the exchange interactions. Our results suggest 4 dmolybdates as an
alternative playground to search for model quantum magnets.
DOI: 10.1103 /PhysRevB.96.024 4 4 5
I. INTRODUCTION
The 4 dtransition-metal oxides naturally bridge the two
different regimes of the strongly correlated 3dcompounds
and the 5 dcompounds with strong spin-orbit coupling (SOC)
[1]. To what extent the 4 dcompounds represent either regime
or display original properties is largely an open question of
current interest [2]. Most notably, for instance, it is intriguing
that seemingly similar Ca2RuO4and Sr2RuO4display totally
different behaviors: the former is a Mott insulator [36],
while the latter is a metal and becomes superconducting at
low temperature [58]. Despite great interest, however, purely
4dquantum (spin-1/2) magnets are rather rare [912]asthe
electronic structure is often complicated by the presence of
other types of 3 dor 4 fmagnetic orbitals [13 ].
Among the few known 4d1magnets [9,11,12]themolyb-
denum phosphate MoOPO4is reported [14 ]. The MoO6
octahedra with Mo5+ions are corner shared to form a chain
along the crystallographic caxis of the tetragonal structure
[Fig. 1(a)], and these chains are further coupled to each
other via corner sharing PO4tetrahedra [Fig. 1(b)][14 ,15 ].
Previous susceptibility data on a powder sample of MoOPO4
shows a Curie-Weiss behavior with antiferromagnetic !CW =
14 .5Kandamagnetictransitionat18K[16]. The 31P
NMR on a powder evidences a substantial exchange through
the PO4tetrahedra, and a sharp powder ESR line infers a
rather isotropic gfactor [16]. However, so far there have not
*minki.jeong@gmail.com
henrik.ronnow@epfl.ch
been any studies on the magnetic structure in the ordered
state or magnetic properties of a single crystal. Moreover,
any discussion on the possible interplay between the crystal
electric field and SOC is absent.
Here we report the magnetic and thermodynamic properties
of a MoOPO4single crystal using specific heat, susceptibility,
magnetization, ESR, and neutron diffraction experiments. We
also elucidate the electronic states and magnetic aspects in
light of SOC and crystal-field effects, with the help of ab initio
quantum-chemistry calculations.
II. EXPERIMENTAL DETAILS
High-quality single crystals of MoOPO4were grown
following the procedure described in Ref. [14 ]. H2MoO4
was mixed with concentrated phosphoric acid and heated
up to 1000 C for reaction in an open platinum crucible.
After being cooled to room temperature, the resulting dark-
blue solid was dissolved in a large amount of hot water.
The yellow transparent crystals were obtained in a platelike
shape [Fig. 1(c)]. Large crystals have a typical dimension
of 3 ×2×0.4mm
3with the caxis normal to the plate.
The crystal belongs to the space group P4/n,withlattice
parameters of a=b=6.204 4 ˚
Aandc=4.3003 ˚
A, obtained
by single-crystal x-ray diffraction, in agreement with Ref. [14 ].
Specific heat was measured using a physical properties
measurement system (PPMS, Quantum Design, Inc.), and
magnetization was measured using a magnetic properties
measurement system (MPMS, Quantum Design, Inc.). ESR
measurements were performed using a Bruker X-band spec-
trometer with a TE102 resonant cavity around 9.4 GHz.
24 69-995 0/2017/96(2)/024 4 4 5 (8) 024 4 4 5 -1 ©2017 American Physical Society
L. YANG et al. PHYSICAL REVIEW B 96,024445 (2017)
FIG. 1. Crystal structure of MoOPO4projected onto (a) the ac
planes, showing a chainlike arrangement of MoO6octahedra (yellow),
and (b) the ab planes, showing the coupling between the chains via
PO4tetrahedra (blue). Dashed lines represent the unit cells. Possible
in-plane (J1and J2) and out-of-plane (Jc)exchangecouplingsare
also shown. (c) Photograph of a representative single crystal.
Neutron diffraction experiments were performed on TRICS
and D23 beamlines at the Paul Scherrer Institute and Institut
Laue-Langevin, respectively. An incident neutron wavelength
of 2.3 109 ˚
A was employed.
III. RESULTS
A. Specific heat
Figure 2(a) shows the specific heat Cpmeasured from 2
to 15 0 K in zero field and in a magnetic field of 14 T. Cp
above 25 K for both fields is essentially the same, increasing
monotonically with increasing temperature. In zero field a
pronounced peak is found at 16.1 K, while the peak is
shifted to a slightly lower temperature of 15.4 K at 14 T.
These peaks correspond to a transition into a magnetically
long range ordered phase, as evidenced by other experimental
measurements discussed in later sections.
In order to extract the magnetic part of the specific heat Cmag
and to deduce the corresponding entropy Smag,wesimulatethe
lattice contribution from the high-temperature data by taking
into account the Debye and Einstein contributions. We fit the
Cpdata above 3 0 K by a lattice-only model, Cp=CD+
!iCE,i, where CDand CE,i represent the Debye and Einstein
terms, respectively. The Debye term is expressed as
CD=9nDR"T
!D#
3$!D/T
0
x4ex
(ex1)2dx, (1)
and the Einstein term is expressed as
CE=3nERy2ey
(ey1)2,y!E/T, (2)
where Rdenotes the gas constant, !Dand !Eare the Debye
and Einstein temperatures, and nDand nEare the numbers of
FIG. 2. (a) Specific heat Cpas a function of temperature in zero
field (circles) and at 14 T (squares). The solid line represents the best
fit of the simulated lattice contribution using the Debye (dash-dotted
line) and Einstein (dotted line) terms. The inset provides an enlarged
view of the low-temperature region. (b) Left axis: magnetic part of
the specific heat Cmag divided by temperature (circles). Right axis:
the solid line is the entropy calculated from Cmag.
the corresponding modes, respectively; the sum nD+nEis the
total number of atoms per formula unit. For our purpose, we
consider that a phenomenological fit using nD,nE,!D,and
!Eas free parameters is sufficient. The best fit for the zero field
was obtained when using one Debye and two Einstein terms,
which yields the characteristic temperatures !D=1177 K,
!E,1=372K, and !E,2=15 4 K and the numbers nD=4,
nE,1=2, and nE,2=1. The solid line in Fig. 2(a) is the
best-fit result for the total lattice contribution, while the
dash-dotted and dotted lines are the corresponding Debye and
Einstein contributions, respectively. While the parameters in
the phenomenological phonon fit may not be directly physical,
they provide a parametrization of the lattice contribution to the
specific heat, which can be substracted to estimate the magnetic
specific heat.
Figure 2(b) shows the resulting Cmag/T in zero field (cir-
cles, left axis) obtained by subtracting the lattice contribution
from the measured Cp. The solid line in Fig. 2(b) plots
Smag(T)obtainedbyintegratingCmag/T over temperature
(right axis). Smag(T)isfoundtoreachandstayatRln 2 at
high temperatures, indicating two-level degrees of freedom.
The thin colored band in Fig. 2(b) represents the entropy range
obtained when fitting the Cpdata by varying the lower bound
of temperature between 25 and 3 5 K to confirm the negligible
dependence of the result on the chosen fit range. A similar
analysis for the 14 T data (not shown) indicates negligible
field effects.
024 4 4 5 -2
J1-J2SQUARE LATTICE . . . PHYSICAL REVIEW B 96,024445 (2017)
FIG. 3. (a) The dc magnetic susceptibility χ(T) in a field of H=0.1 T applied parallel (circles) and perpendicular (squares) to the c
axis. The dashed line represents the Curie-Weiss fit for Hc, and the solid line shows the high-temperature series expansion using the Padé
approximant (see the text). The inset shows an enlarged view of the low-temperature region. (b) Isothermal magnetization M(H)forHc
(solid symbols) and Hc(open symbols) at several different temperatures. The inset plots the field derivative dM/dH versus Hfor Hc.
(c) Magnetic phase diagram from the susceptibility (squares), specific heat (upward triangles), magnetization (circles), and neutron diffraction
(downward triangles) data. Lines are guides to the eye. The colored background represents the result from the mean-field calculations (see
text).
B. Susceptibility and magnetization
Figure 3(a) shows the dc magnetic susceptibility χ=
M/H, where Mis magnetization, in a field of H=0.1T
applied parallel and perpendicular to the caxis. For both cases,
χ(T)showsalmostidenticalbehaviorfrom300downto20K.
However, for Hc,χ(T) exhibits a sharp drop toward zero as
temperature is decreased across 17 K, while the one for Hc
remains only weakly temperature dependent. This is indicative
of an antiferromagnetic transition where the ordered moments
at low temperatures are collinear to each other and parallel to
the caxis.
The nearly isotropic, high-temperature part of χ(T)could
be well fit by the Curie-Weiss formula, χ(T)=C/(T
!CW )+χ0,where!CW is the Curie-Weiss temperature and
χ0is a temperature-independent diamagnetic and background
term that may arise from the plastic sample holder or the small
amount of grease used. The best and stable fit is obtained
in the 5 0–3 00 K range, which yields the effective moment
µeff =1.67(1)µBper Mo5+ion, !CW =6(1) K, and χ0=
2.2(1) ×104emu/mol for Hcand µeff =1.69(1)µB,
!CW =4(1)K,andχ0=4.6(1) ×104emu/mol for H
c.ThebestfitforHcis shown as a dashed line in
Fig. 3(a). The negative !CW indicates that antiferromagnetic
interactions are dominant. The effective moments indicate a
spin-only value consistent with the specific-heat results.
The isothermal magnetization M(H)forHcand Hc
at several temperatures is shown in Fig. 3(b).At5 K,M(H)
increases slowly with the field Hcup to 3 T but then sharply
increases in a narrow field range of 3 –4 T until it eventually
converges to the high-temperature M(H)dataobtainedat16or
20 K. This stepwise increase of M(H)becomessmearedoutas
temperature is increased. On the other hand, no such stepwise
behavior was observed at any temperatures for Hc.These
are typical signatures of a spin-flop transition which occurs
when the field is applied along an easy axis, along which
the ordered moments align: the spins on the two sublattices
rotate to attain components perpendicular to the applied field
direction as a result of competition between antiferromagnetic
coupling, magnetic anisotropy, and the Zeeman energy.
The magnetic phase diagram is thus mapped out by combin-
ing the above bulk magnetic and specific-heat results, as shown
in Fig. 3(c).Theantiferromagnetictransitiontemperaturesin
different fields are obtained from the peaks in χ(T)andCp(T),
and the spin-flop transition fields at different temperatures are
obtained from the peak positions in the dM/dH versus Hplot
[inset of Fig. 3(b)].
C. Electron spin resonance
In order to gain microscopic insight into the magnetic
properties, we have performed ESR measurements as a
function of field orientation and temperature. Figure 4(a)
plots the obtained room-temperature gfactor as the field
direction is rotated by φin the ab and ac planes. The g
factor in the ac plane shows a φvariation as large as 2%
with characteristic cos2φangular dependence. On the other
hand, the gfactor in the ab plane remains essentially constant,
as expected from the tetragonal symmetry, within the error of
0.08%, which might have arisen from a slight misorientation
of the crystal. We obtain the gfactor along the principal
axes as ga=1.926(2) and gc=1.889(2). The average value
g=(2ga+gc)/3=1.913 (2) agrees with the one previously
obtained by powder ESR [17]. These gvalues correspond to
the effective moments of 1.64 µBand 1.66µBfor spin-1/2for
Hcand Hc,respectively,whichareveryclosetothe
effective moment values obtained from the Curie-Weiss fit in
the previous section.
For a system with tetragonal symmetry with short distances
between the transition-metal and ligand ions, one would expect
ga<g
c[18]. However, we find an opposite structure for the g
024 4 4 5 -3
L. YANG et al. PHYSICAL REVIEW B 96,024445 (2017)
FIG. 4. (a) Angular dependence of the gfactor at room temperature from the ESR measurements, where solid symbols are for the field
orientation varied on the ac plane and open symbols are for the field orientation varied on the ab plane. (b) Resonance field B0(solid circles,
right axis) and linewidth $B0(open circles, left axis) of the ESR spectrum as a function of temperature. The inset plots normalized spin
susceptibility χs(T)/χs(3 00 K) as a function of temperature. (c) Temperature evolution of the spectrum for Bcacross the transition (open
circles). The solid line is a sum of two contributions from intrinsic (dotted line) and defect (dashed line) susceptibilities. At 5 K, the data for
Bc(solid circles) are overlaid.
factor in MoOPO4, even though the orbital energy diagram for
the Mo5+ion is expected to be similar to that of tetragonally
compressed octahedron with a stabilized dxy orbital (see Fig. 7
below). As explained in Sec. III E,themultiorbitalcharacterof
the ground state in MoOPO4results in the observed gvalues.
Figure 4(b) shows the temperature dependence of the
resonance field B0and the linewidth $B0of the ESR spectrum.
B0slowly decreases as temperature is lowered from 300 down
to 24 K, which may be attributed to a lattice contraction.
As temperature is further lowered below 24 K, B0starts
increasing sharply, which indicates that a magnetic transition is
approached. Similarly, $B0slowly decreases as temperature is
lowered down to 25 K but then starts broadening significantly
as temperature is further lowered down to 15 K due to critical
spin fluctuations. The inset of Fig. 4(b)plots the temperature
dependence of the local spin susceptibility, which is obtained
from the spectral area at each temperature normalized by
the one at 3 00 K, χs(T)/χs(3 00 K). The data could be fit
to the Curie-Weiss formula with !CW =8.9 K, which is in
reasonable agreement with the bulk susceptibility result shown
in Fig. 3(a).
Across the transition, the ESR line changes in shape and
intensity as shown in Fig. 4(c).Thelinesustainsaperfect
Lorentzian shape down to 16 K. On the other hand, the
line below 16 K close to the transition fits better to a
sum of two Lorentzians: one corresponds to the intrinsic
sample susceptibility, while the other may correspond to
some defects. Indeed, the ESR signal at the paramagnetic
resonance field position below 15 K corresponds to about
0.1% concentration of paramagnetic impurities. The response
below 15 K represents the summation of the possible defect
contribution and the intrinsic susceptibility. The tiny intrinsic
response below the transition temperature may represent
clusters of spins that continue to fluctuate within the ESR time
window, which essentially disappears at lower temperatures
below 14 K. At 5 K, a broad hump of weak signal is observed
around 0.27 T for Bcwhich is absent for Bc.Thissignal
may correspond to an antiferromagnetic resonance.
D. Neutron diffraction
To determine the microscopic magnetic structure, we
have performed neutron diffraction measurements. Magnetic
intensity appears at the position of the k=(100) wave vector at
5K,asshownintherotationscaninFig.5(a).Noappreciable
change in scattering is found close to (001) between 5 and 25 K,
as shown in Fig. 5(b). A small shoulder of the (001) reflection
is likely to originate from a closely oriented secondary grain.
Anonzero(100)reectionwouldbeconsistentwithMospins
FIG. 5 . Neutron diffraction measurements of rotation scans
through (a) (100) and (b) (001) reflections recorded at 5 and 25 K.
(c) Temperature evolution of the Bragg peak integrated intensity. The
solid line is a power-law fit I(T)(TNT)2βwith the parameters
β=0.23 and TN=16.17 ±0.06 K. (d) The (010) peak counts as a
function of magnetic field parallel to the caxis.
024 4 4 5 -4
J1-J2SQUARE LATTICE . . . PHYSICAL REVIEW B 96,024445 (2017)
FIG. 6. Schematic phase diagram of the spin-1/2J1-J2Heisen-
berg model on a square lattice with corresponding compounds
[12]. Different ground states are expected depending on the J2/J1
ratio as represented in the diagram, where CAF, NAF, and FM
refer to columnar antiferromagnetic, Néel antiferromagnetic, and
ferromagnetic ground states, respectively. The present compound,
MoOPO4,extendsthematerialsinvestigationfarintotheNAFregime.
related by a spatial inversion being antiparallel. Due to the
dipolar nature of the magnetic interaction, only magnetization
perpendicular to the scattering wave vector gives a nonzero
structure factor. As no change is observed for the (001)
reflection upon cooling below TN,wecanconcludethatthe
moments are parallel to the caxis. To verify that this is
consistent with the symmetry of the lattice and rule out any
other magnetic structures, we utilize BASIREPS [19]andoutline
the results here.
The magnetic representation is decomposed into six one-
dimensional irreducible representations &νwhose resulting
basis functions are shown in Table I. Examining the results
of the irreducible magnetic representations, we find that only
&2is consistent with our observations. These results are in
contrast to the closely related AMoO(PO4)Cl (A=KandRb)
materials. Unlike the tilted arrangement of MoO6octahedra
d
xy
dyz,x
z
d
x2
y2
d
3z
2
r
2
t
2g
eg
FIG. 7. Single-particle energy-level diagram of dstates in an
octahedral arrangement of the oxygen ligands (in red) and Mo ion (in
yellow) in MoOPO4.
TABLE I. Basis functions of irreducible representation &νfor
k=(100) separated into real (Re) and imaginary (Im) components
and resolved along the crystallographic axes. The two equivalent Mo1
and Mo2ions are related by an inversion through the origin.
νMo1Mo2
1 Re (0,0,1) (0,0,1)
2 Re (0,0,1) (0,0,¯
1)
3 Re (1,0,0) (1,0,0)
3 Im (0,¯
1,0) (0,¯
1,0)
4 Re (1,0,0) (¯
1,0,0)
4 Im (0,¯
1,0) (0,1,0)
5 Re (1,0,0) (1,0,0)
5 Im (0,1,0) (0,1,0)
6 Re (1,0,0) (¯
1,0,0)
6 Im (0,1,0) (0,¯
1,0)
and PO4tetrahedra in MoOPO4,AMoO(PO4)Cl possesses a
higher symmetry where the octahedra and tetrahedra are ar-
ranged untilted in the abplane [20]. Powder neutron diffraction
measurements on AMoO(PO4)Cl reveal an antiferromagnetic
structure where Mo moments are instead confined to the ab
plane [12].
Figure 5(c) shows the temperature dependence of the
(100) Bragg peak integrated intensity. By fitting a power-law
dependence to the intensity, we find TN=16.17 ±0.06 K,
which is consistent with the magnetization and specific-
heat measurements. The order parameter exponent is found
to be β=0.23 , corresponding to the two-dimensional XY
universality class. However, dedicated measurements with
better resolution and separating critical scattering would be
needed before any conclusions could be drawn from this. In
Fig. 5(d) we show the magnetic Bragg peak intensity as a
function of applied field along the caxis recorded at 2 K. Above
3T,wendasharpdecreaseinintensitywhichthenappears
to saturate above 5 T. The change in the Bragg peak intensity
is consistent with a spin-flop transition that is observed in
the magnetization measurements shown in Fig. 3(b). This
corresponds to a tilt of the moments by approximately 3 5
away from the caxis for the fields above 5 T.
E. Model calculations
In order to gain insight into the magnetic interactions,
we fit the experimental susceptibility shown in Fig. 3(a)
using a high-temperature series expansion [21] assuming a
J1-J2spin-1/2 Heisenberg model on a square lattice. The
best fit [solid line in Fig. 3(a)] returns J1=11.4(0.4)K
and J2=5.2(1.0) K, corresponding to J2/J1=0.46.This
ratio supports a collinear Néel order for the ground state (see
Fig. 6) in agreement with the neutron diffraction result. Using
the mean-field expression for the Curie-Weiss temperature,
!CW =S(S+1)
3kB%
i=1,2
ziJi,(3 )
where ziis the number of neighbors for the corresponding
couplings (4 for both J1and J2in the present case), the high-
temperature expansion fit yields !CW =6.2K,whichagrees
with the value obtained from the simple Curie-Weiss fit. Next,
024 4 4 5 -5
L. YANG et al. PHYSICAL REVIEW B 96,024445 (2017)
we simulate the phase diagram using a mean-field calculation.
The results are presented by the colored background in
Fig. 3(c).Aslightexchangeanisotropy,$=0.02, has been
introduced in the Hamiltonian,
H=J1%
i,j&Sx
iSx
j+Sy
iSy
j+(1 +$)Sz
iSz
j'
+J2%
i,k&Sx
iSx
k+Sy
iSy
k+Sz
iSz
k',(4 )
where i,jand i,krefer to the nearest and the next-nearest
neighbors in the abplane, to account for the spin-flop transition
in a spin-1/2systemwheresingle-ionanisotropyisnot
expected to be present. We note that the mean-field calculation
reproduces the temperature dependence of the spin-flop field.
From the mean-field expression for the Néel temperature,
TN=S(S+1)
3kB%
i=1,2
zi(1)iJi,(5 )
we obtain TN=16.6(1.4)K, whichis in excellent agreement
with the actual value from the experiments. In the above
analyses, we do not include Jcexplicitly: although an ar-
bitrarily small Jcis necessary in the actual system to give
rise to the (three-dimensional) long-range magnetic ordering,
including this parameter in the mean-field calculation produces
an insignificant change in the phase diagram. In addition,
Jcconnects only two neighbors instead of the four of the
other couplings in the ab plane, and thus its effect should be
correspondingly weaker.
Our methods of analysis do not necessarily select the best
model, but rather test the validity and consistency of a proposed
one. For instance, ferromagnetic Jccomparable in strength
to antiferromagnetic J1, with negligible J2, may similarly
reproduce our experimental data. However, the ground-state
wave function from our ab initio quantum-chemistry calcula-
tions (see the next section) indicates zero contribution from
the out-of-plane orbitals and thus no direct virtual hopping
channels for Jcto be appreciable, in contrast to the other
coupling on the ab plane.
With strong ferromagnetic second-nearest-neighbor inter-
actions, MoOPO4populates a region of the J1-J2phase
diagram which has so far seen rather few investigations (see
Fig. 6). In the context of (π,0) zone-boundary anomalies on
the square lattice, linear spin-wave theory would for MoOPO4
predict a dispersion with significantly higher energy at (π,0)
than at (π/2,π/2), opposite the case of weak antiferromagnetic
J2in Cu(pz)2(ClO4)2[22]. Compared to the 3 9% reduction in
ordered moment due to quantum fluctuations for the nearest-
neighbor Heisenberg model, the estimate for J2/J1=0.46
is only a 24 % reduction of the ordered moment. Adding
the weak anisotropy for MoOPO4yields a 21% reduction in
ordered moment. Hence quantum fluctuations are likely much
weaker in MoOPO4than in, e.g., Cu(DCOO)2·4D
2O, called
CFTD for short [23 26]orSr
2CuTeO6[27], and it would be
interesting in future investigations to examine whether this
leads to a similar suppression of the quantum dispersion and
continuum around (π,0).
TABLE II. Relative energies of d-level states of the Mo5+ion
obtained from CASSCF/NEVPT2 calculations. The corresponding
wave functions without (coefficients) and with (weights) SOC at
the CASSCF level are also provided, where the up and down arrows
signify the Szvalues of +1
2and 1
2,respectively[41]. At the NEVPT2
level, the wave function would also contain contributions from the
inactive and virtual orbitals. For simplicity only the weights of the
SOC wave function are provided as the coefficients are complex.
t1
2gStates Relative Wave function (CASSCF)
without SOC energies (eV) coefficients
|φ000.95 |xy⟩−0.32|x2y2
|φ11.79 0.98 |yz+0.21 |zx
|φ21.79 0.21 |yz⟩−0.98 |zx
|φ33.68 0.32|xy +0.95 |x2y2
|φ44.42 1.00 |z2
t1
2gStates Relative Wave function (CASSCF)
with SOC energy (eV) normalized weights (%)
|ψ0086.0|φ0,↑⟩ +14 .0|φ0,↓⟩
|ψ11.75 5 0.0|φ1,↑⟩ +50.0|φ2,↓⟩
|ψ21.82 4 6.0|φ1,↑⟩ +46.0|φ2,↑⟩
+4.0|φ1,↓⟩ +4.0|φ2,↓⟩
|ψ33.70 88.0|φ3,↑⟩ +12.0|φ3,↓⟩
|ψ44.44 100.0|φ4
F. Ab initio calculations
An interesting feature in MoOPO4is that the axial position
of the Mo4+ion inside the MoO6octahedron is heavily shifted
such that the short and long distances to the apical oxygens
are 1.65 2 and 2.64 1 ˚
A, respectively. As a consequence, the
octahedral symmetry around the Mo ion is reduced, resulting
in the removal of octahedral orbital degeneracies and an
orbitally mixed electronic ground state. To elucidate the
electronic levels of the Mo5+ion in low-symmetry crystal
fields in MoOPO4, we performed ab initio quantum-chemistry
calculations using the cluster-in-embedding formalism [28].
AclusterofasingleactiveMoO
6octahedron along with
surrounding nearest-neighbor (NN) PO4tetrahedra within the
plane and the out-of-plane MoO6octahedra embedded in an
array of point charges that reproduces the effect of the solid
environment [29] was considered for many-body calculations.
The NN polyhedra were included within the cluster region
to better describe the charge density within the active MoO6
region. Such calculations have provided excellent insights into
the interplay of crystal field and SOC effects for several 4d
and 5 dtransition-metal compounds [3033].
A perfect octahedral arrangement of the oxygen ligands
around the transition-metal ion splits the dlevels into high-
energy egand low-energy t2gmanifolds (see Fig. 7). In
MoOPO4,thelow-symmetrycrystalfieldsfurthersplitthe
t2gand eglevels of the Mo5+ion, resulting in an orbital singlet
ground state. In Table II the ground-state wave function and the
d-dexcitations of the Mo5+ion are summarized. These were
obtained from many-body multiconfigurational self-consistent
field (MCSCF) [34]andN-electron valence-state perturbation
theory (NEVPT2) [35]calculationsfortheatomsintheactive
cluster region. All-electron Douglas-Kroll-Hess (DKH) basis
sets of triple-zeta quality [36]wereusedtorepresentthe
024 4 4 5 -6
J1-J2SQUARE LATTICE . . . PHYSICAL REVIEW B 96,024445 (2017)
TABLE III. Computed gfactors of MoOPO4at the NEVPT2
level of theory. The ground-state multiconfiguration wave function as
shown in Table II produces the correct structure for the gfactors.
CASSCF gagc
active orbital space
t2g1.91 1.99
t2g+eg1.92 1.84
Mo and oxygen ions in the central MoO6octahedron, and
for the Mo and P ions in the NN polyhedra we employed
effective core potentials [37,38]withvalencetriple-zeta[37]
and a single basis function, respectively. The oxygen ions
corresponding to the NN MoO6and PO4polyhedra were
expanded in two sand one patomic natural orbital type [39]
functions. All the calculations were performed using the ORCA
quantum-chemistry package [40].
In the complete active space formalism of the MCSCF
(CASSCF) calculation, a self-consistent wave function was
constructed with an active space of one electron in five Mo
dorbitals. On top of the CASSCF wave function, NEVPT2
was applied to capture the dynamic electronic correlation.
Table II shows that the ground state is predominantly of dxy
character but has significant contributions from the dx2y2
orbital. The first orbital excitations are nearly degenerate at
1.79 eV and are composed of dyz-anddzx -like orbitals. This
scenario is in contrast to the situation in other t2g-active class
of compounds with regular transition-metal oxygen octahedra
where the t2gmanifold remains degenerate with an effective
orbital angular momentum ˜
l=1. In the latter scenario the
spin-orbit interaction admixes all the t2gstates to give rise to
atotalangularmomentumJeff ground state [42,43]. Due to
the large noncubic crystal-field splittings in the t2gmanifold in
MoOPO4,thespin-orbitinteractionhasanegligibleeffecton
the Mo5+ground state ψ0(see the with SOC results in Table II).
However, the orbital angular momentum is unquenched in
dzx and dyz, and hence the SOC results in the splitting of
the high-energy states ψ1and ψ2. Our calculations result in
excitation energies of 3.68 and 4 .42 eV into the egstates.
To understand the unusual structure of gfactors deduced
from the ESR experiments, we computed them from the
ab initio wave function as implemented in ORCA [44]. In
Table III,thegfactors obtained from CASSCF calculations
with two different active orbital spaces, only t2gand t2g+eg,
are presented. With only t2gorbitals in the active space, we
find ga<g
cas expected for tetragonal symmetry with the
dxy -like orbital occupied in the ground state. By enlarging the
active space, the wave function now contains configurations
involving the egorbitals as well, and this is crucial to produce
the experimentally observed gfactors with ga>g
c.
IV. CONCLUSION
We have show n with a va r iety of exp e rimental a n d
computational techniques that MoOPO4realizes a spin-1/2
magnetic system of 4 d1electrons, with the quenched orbital
moment due to the large displacement of the Mo ions inside
the MoO6octahedra. The magnetic ground state supports a
Néel-type collinear staggered order on the square lattice with
the moments pointing normal to the plane, while the moments
align ferromagnetically along the stacking axis. The compound
likely realizes a spin-1/2HeisenbergmodelonaJ1-J2square
lattice, with an unfrustrated configuration of antiferromagnetic
J1and ferromagnetic J2, while a small interlayer coupling
Jcwould lead to the observed magnetic ordering transition.
The spin-flop transition suggests a small easy-axis anisotropy
in the dominant antiferromagnetic exchange, and the mean-
field calculation reproduces the experimental magnetic phase
diagram. The small anisotropy in the gfactor observed in ESR,
which is reproduced by the quantum-chemistry calculations,
indicates that the ground state involves the higher-energy eg
orbitals in addition to the t2gorbitals. Our results suggest that
4dmolybdates provide an alternative playground to search for
model quantum magnets other than 3 dcompounds.
ACKNOWLEDGMENTS
We tha n k R. Scopell i ti and O. Zaha r ko for thei r h elp with
x-ray and neutron diffraction, respectively. We also thank
V. Fav re a n d P. H u a n g f o r th e i r h e l p wi t h t h e s p ec i c - h ea t
analysis. V.M.K. is grateful to H. Stoll for discussions on
effective core potentials. This work was supported by the
Swiss National Science Foundation, the MPBH network,
and European Research Council grants CONQUEST and
TopoMat (No. 3 065 04 ). M.J. is grateful for support from the
European Commission through the Marie Skłodowska-Curie
Action COFUND (EPFL Fellows). M.K. is supported by a
Grant-in-Aid for Scientific Research (C) (JSPS, KAKENHI
No. 15 K05 14 0). The ab initio calculations were performed
at the Swiss National Supercomputing Centre (CSCS) under
project s675 .
[1] D. Khomskii, Transition Metal Compounds (Cambridge Uni-
versity Press, Cambridge, 2014 ).
[2] W. Witczak-Krempa, G. Chen, Y. B. Kim, and L. Balents, Annu.
Rev. Condens. Matter Phys. 5,57(2014 ).
[3 ] S. Nakatsuji, S.-i. Ikeda, and Y. Maeno, J. Phys. Soc. Jpn. 66,
1868 (1997).
[4 ] G. Cao, S. McCall, M. Shepard, J. E. Crow, and R. P. Guertin,
Phys. Rev. B 56,R2916(R) (1997).
[5 ] S. Nakatsuji and Y. Maeno, Phys. Rev. Lett. 84,2666 (2000).
[6] C. G. Fatuzzo, M. Dantz, S. Fatale, P. Olalde-Velasco, N. E.
Shaik, B. D. Piazza, S. Toth, J. Pelliciari, R. Fittipaldi, A.
Vecchione, N. Kikugawa, J. S. Brooks, H. M. Rønnow, M.
Grioni, Ch. Rüegg, T. Schmitt, and J. Chang, Phys. Rev. B
91 ,15 5 104 (2015 ).
[7] Y. Maeno, H. Hashimoto, K. Yoshida, S. Nishizaki, T. Fujita, J.
Bednorz, and F. Lichtenberg, Nature (London) 372 ,532(1994 ).
[8] K. Ishida, H. Mukuda, Y. Kitaoka, K. Asayama, Z. Mao, Y.
Mori, and Y. Maeno, Nature (London) 396,65 8 (1998).
[9] M. A. de Vries, A. C. Mclaughlin, and J.-W. G. Bos, Phys. Rev.
Lett. 104,177202 (2010).
[10] T. Aharen, J. E. Greedan, C. A. Bridges, A. A. Aczel, J.
Rodriguez, G. MacDougall, G. M. Luke, T. Imai, V. K.
024 4 4 5 -7
L. YANG et al. PHYSICAL REVIEW B 96,024445 (2017)
Michaelis, S. Kroeker, H. Zhou, C. R. Wiebe, and L. M. D.
Cranswick, Phys. Rev. B 81 ,224 4 09 (2010).
[11] L. Clark, G. J. Nilsen, E. Kermarrec, G. Ehlers, K. S. Knight, A.
Harrison, J. P. Attfield, and B. D. Gaulin, Phys. Rev. Lett. 113,
117201 (2014 ).
[12] H. Ishikawa, N. Nakamura, M. Yoshida, M. Takigawa, P.
Babkevich, N. Qureshi, H. M. Rønnow, T. Yajima, and Z. Hiroi,
Phys. Rev. B 95,064 4 08 (2017).
[13 ] J. S. Gardner, M. J. P. Gingras, and J. E. Greedan, Rev. Mod.
Phys. 82 ,53 (2010).
[14 ] P. Kierkegaard and J. M. Longo, Acta Chem. Scand. 24,427
(1970).
[15 ] E. Canadell, J. Provost, A. Guesdon, M. Borel, and A. Leclaire,
Chem. Mater. 9,68 (1997).
[16] L. Lezama, K. Suh, G. Villeneuve, and T. Rojo, Solid State
Commun. 76,449(1990).
[17] L. Lezama, G. Villeneuve, M. Marcos, J. Pizarro, P. Ha-
genmuller, and T. Rojo, Solid State Commun. 70,899
(1989).
[18] A. Abragam and B. Bleaney, Electron Paramagnetic Resonance
of Transition Ions (Clarendon, Oxford, 1970).
[19] J. Rodríguez-Carvajal, Phys. B (Amsterdam, Neth.) 192,55
(1993 ).
[20] M. Borel, A. Leclaire, J. Chardon, J. Provost, and B. Raveau,
J. Solid State Chem. 137,214 (1998).
[21] H.-J. Schmidt, A. Lohmann, and J. Richter, Phys. Rev. B 84,
104 4 4 3 (2011).
[22] N. Tsyrulin, F. Xiao, A. Schneidewind, P. Link, H. M. Rønnow,
J. Gavilano, C. P. Landee, M. M. Turnbull, and M. Kenzelmann,
Phys. Rev. B 81 ,13 4 4 09 (2010).
[23 ] H. M. Rønnow, D. F. McMorrow, and A. Harrison, Phys. Rev.
Lett. 82 ,3152 (1999).
[24 ] H. M. Rønnow, D. F. McMorrow, R. Coldea, A. Harrison, I. D.
Youngson, T. G. Perring, G. Aeppli, O. Syljuåsen, K. Lefmann,
and C. Rischel, Phys. Rev. Lett. 87,03 7202 (2001).
[25 ] N. B. Christensen, H. M. Rønnow, D. F. McMorrow, A. Harrison,
T. Perring, M. Enderle, R. Coldea, L. Regnault, and G. Aeppli,
Proc. Natl. Acad. Sci. USA 104,15 264 (2007).
[26] B. Dalla Piazza, M. Mourigal, N. B. Christensen, G. Nilsen, P.
Tregenna-Piggott, T. Perring, M. Enderle, D. F. McMorrow, D.
Ivanov, and H. M. Rønnow, Nat. Phys. 11,62 (2015 ).
[27] P. Babkevich, V. M. Katukuri, B. Fåk, S. Rols, T. Fennell, D.
Paji´
c, H. Tanaka, T. Pardini, R. R. P. Singh, A. Mitrushchenkov,
O. V. Yazyev, and H. M. Rønnow, Phys. Rev. Lett. 117,23 7203
(2016).
[28] L. Hozoi and P. Fulde, in Computational Methods for Large
Systems, edited by J. R. Reimers (Wiley, Hoboken, NJ, 2011),
pp. 201–224 .
[29] M. Klintenberg, S. Derenzo, and M. Weber, Comput. Phys.
Commun. 131,120 (2000).
[3 0] V. M. Katukuri, K. Roszeitis, V. Yushankhai, A.
Mitrushchenkov, H. Stoll, M. van Veenendaal, P. Fulde,
J. van den Brink, and L. Hozoi, Inorg. Chem. 53,4833 (2014 ).
[3 1] V. M. Katukuri, H. Stoll, J. van den Brink, and L. Hozoi, Phys.
Rev. B 85,2204 02(R) (2012).
[3 2] N. A. Bogdanov, V. M. Katukuri, H. Stoll, J. van den Brink, and
L. Hozoi, Phys. Rev. B 85,23 5 14 7 (2012).
[3 3 ] X. Liu, V. M. Katukuri, L. Hozoi, W.-G. Yin, M. P. M. Dean,
M. H. Upton, J. Kim, D. Casa, A. Said, T. Gog, T. F. Qi, G. Cao,
A. M. Tsvelik, J. van den Brink, and J. P. Hill, Phys. Rev. Lett.
109
,15 74 01 (2012).
[3 4 ] T. Helgaker, P. Jørgensen, and J. Olsen, Molecular Electronic-
Structure Theory (Wiley, Chichester, UK, 2000).
[3 5 ] C. Angeli, R. Cimiraglia, and J.-P. Malrieu, Chem. Phys. Lett.
350,297 (2001).
[3 6] D. A. Pantazis, X.-Y. Chen, C. R. Landis, and F. Neese, J. Chem.
Theory Comput. 4,908 (2008).
[3 7] K. A. Peterson, D. Figgen, M. Dolg, and H. Stoll, J. Chem. Phys.
126,124 101 (2007).
[3 8] G. Igel-Mann, H. Stoll, and H. Preuss, Mol. Phys. 65,13 21
(1988).
[3 9] K. Pierloot, B. Dumez, P.-O. Widmark, and B. Roos, Theor.
Chim. Acta 90,87 (1995 ).
[4 0] F. Neese, WIREs Comput. Mol. Sci. 2,73 (2012).
[4 1] The spin-orbit coupling results in an admixture of the t2gstates
with different Sz; see Ref. [18].
[4 2] B. J. Kim, H. Ohsumi, T. Komesu, S. Sakai, T. Morita, H. Takagi,
and T. Arima, Science 32 3,13 29 (2009).
[4 3 ] B. J. Kim, H. Jin, S. J. Moon, J.-Y. Kim, B.-G. Park, C. S. Leem,
J. Yu, T. W. Noh, C. Kim, S.-J. Oh, J.-H. Park, V. Durairaj, G.
Cao, and E. Rotenberg, Phys. Rev. Lett. 101,0764 02 (2008).
[4 4 ] F. Neese, Mol. Phys. 105,25 07 (2007).
024 4 4 5 -8
... It is interesting to note that recently the compound was successfully fabricated in the form of a single layer [24]. We note many other candidates for the S = 1/2 square antiferromagnets, e.g., Sr 2 CuTeO 6 [25], MoOPO 4 [26], and Ba 2 CuTeO 6 and Ba 2 CuWO 6 [27]. For three-dimensional systems, per-S systems, it reads P R = 1 2π Im log e i 2π L L r=1 rŝ z r mod 1 (S = 0, 1, · · · ) 1 4π Im log e i 4π L L r=1 rŝ z r mod 1 2 (S = 1 2 , 3 2 , · · · ) (A1) See Ref. [32] for the details of these formulas. ...
Preprint
Recent studies revealed that the electric multipole moments of insulators result in fractional electric charges localized to the hinges and corners of the sample. We here explore the magnetic analog of this relation. We show that a collinear antiferromagnet with spin $S$ defined on a $d$-dimensional cubic lattice features fractionally quantized magnetization $M_{\text{c}}^z=S/2^d$ at the corners. We find that the quantization is robust even in the presence of gapless excitations originating from the spontaneous formation of the N\'eel order, although the localization length diverges, suggesting a power-law localization of the corner magnetization. When the spin rotational symmetry about the $z$ axis is explicitly broken, the corner magnetization is no longer sharply quantized. Even in this case, we numerically find that the deviation from the quantized value is negligibly small based on quantum Monte Carlo simulations.
... We simulate the lattice contribution from the high temperature data by taking into account both the Debye (C D ) and Einstein (C E ) contributions, i.e. C lattice =C D +C E [35]. Details related to the method we used to analyze heat capacity data are given in the Supplementary Material [34]. ...
Preprint
The magnetic and structural properties of polycrystalline Co$_{4-x}$ Ni$_x$ Nb$_2$ O$_9$ (x=1,2) have been investigated by neutron powder diffraction, magnetization and heat capacity measurements, and density functional theory (DFT) calculations. For x=1, the compound crystallizes in the trigonal P$\bar{3}$c1 space group. Below T$_N$ = 31 K it develops a weakly non-collinear antiferromagnetig structure with magnetic moments in the ab-plane. The compound with x=2 has crystal structure of the orthorhombic Pbcn space group and shows a hard ferrimagnetic behavior below T$_C$ =47 K. For this compound a weakly non-collinear ferrimagnetic structure with two possible configurations in ab plane was derived from ND study. By calculating magnetic anisotropy energy via DFT, the ground-state magnetic configuration was determined for this compound. The heat capacity study in magnetic fields up to 140 kOe provide further information on the magnetic structure of the compounds.
... We use a combined fit to describe the C p and the volume of the unit cell obtained from x-ray diffraction by a phonon (lattice only) model. Similarly to what has been done in 40,41 , the lattice contribution to the specific heat is given by ...
Preprint
We report magnetic properties of a 3d$^9$ (Cu$^{2+}$) magnetic insulator Cu2OSO4 measured on both powder and single crystal. The magnetic atoms of this compound form layers, whose geometry can be described either as a system of chains coupled through dimers or as a Kagom\'e lattice where every 3rd spin is replaced by a dimer. Specific heat and DC-susceptibility show a magnetic transition at 20 K, which is also confirmed by neutron scattering. Magnetic entropy extracted from the specific heat data is consistent with a $S=1/2$ degree of freedom per Cu$^{2+}$, and so is the effective moment extracted from DC-susceptibility. The ground state has been identified by means of neutron diffraction on both powder and single crystal and corresponds to a $\sim120$ degree spin structure in which ferromagnetic intra-dimer alignment results in a net ferrimagnetic moment. No evidence is found for a change in lattice symmetry down to 2 K. Our results suggest that \sample \ represents a new type of model lattice with frustrated interactions where interplay between magnetic order, thermal and quantum fluctuations can be explored.
... Systems based on the S = 1/2 Heisenberg frustrated square lattice (FSL) model, for example, are extensively studied as they provide a rich magnetic phase diagram depending on the degree of frustration between exchange interactions along the sides, J 1 , and across the diagonal, J 2 , of the square net. For the antiferromagnetic phase diagram 4 , theoretical predictions for the development of Néel and columnar antiferromagnetic orders within the respective dominant J 1 or J 2 regimes have been experimentally established in several materials [5][6][7][8][9][10][11][12][13] . Intriguingly, at the border of these two regimes, materials in which the degree of frustration is maximized-i.e. ...
Preprint
We report the crystal structures and magnetic properties of two psuedo-polymorphs of the $S=1/2$ Ti$^{3+}$ coordination framework, KTi(C$_2$O$_4$)$_2\cdot$xH$_2$O. Single-crystal X-ray and powder neutron diffraction measurements on $\alpha$-KTi(C$_2$O$_4$)$_2\cdot$xH$_2$O confirm its structure in the tetragonal $I4/mcm$ space group with a square planar arrangement of Ti$^{3+}$ ions. Magnetometry and specific heat measurements reveal weak antiferromagnetic interactions, with $J_1\approx7$ K and $J_2/J_1=0.11$ indicating a slight frustration of nearest- and next-nearest-neighbor interactions. Below $1.8$ K, $\alpha$ undergoes a transition to G-type antiferromagnetic order with magnetic moments aligned along the $c$ axis of the tetragonal structure. The estimated ordered moment of Ti$^{3+}$ in $\alpha$ is suppressed from its spin-only value to $0.62(3)~\mu_B$, thus verifying the two-dimensional nature of the magnetic interactions within the system. $\beta$-KTi(C$_2$O$_4$)$_2\cdot$2H$_2$O, on the other hand, realises a three-dimensional diamond-like magnetic network of Ti$^{3+}$ moments within a hexagonal $P6_222$ structure. An antiferromagnetic exchange coupling of $J\approx54$ K -- an order of magnitude larger than in $\alpha$ -- is extracted from magnetometry and specific heat data. $\beta$ undergoes N\'eel ordering at $T_N=28$ K, with the magnetic moments aligned within the $ab$ plane and a slightly reduced ordered moment of $0.79~\mu_B$ per Ti$^{3+}$. Through density-functional theory calculations, we address the origin of the large difference in the exchange parameters between the $\alpha$ and $\beta$ psuedo-polymorphs. Given their observed magnetic behaviors, we propose $\alpha$-KTi(C$_2$O$_4$)$_2\cdot$xH$_2$O and $\beta$-KTi(C$_2$O$_4$)$_2\cdot$2H$_2$O as close to ideal model $S=1/2$ Heisenberg square and diamond lattice antiferromagnets, respectively.
Article
Recent studies revealed that the electric multipole moments of insulators result in fractional electric charges localized to the hinges and corners of the sample. We here explore the magnetic analog of this relation. We show that a collinear antiferromagnet with spin S defined on a d-dimensional cubic lattice features fractionally quantized magnetization Mcz=S/2d at the corners. We find that the quantization is robust even in the presence of gapless excitations originating from the spontaneous formation of the Néel order, although the localization length diverges, suggesting a power-law localization of the corner magnetization. When the spin rotational symmetry about the z axis is explicitly broken, the corner magnetization is no longer sharply quantized. Even in this case, we numerically find that the deviation from the quantized value is negligibly small based on quantum Monte Carlo simulations.
Article
We report results of magnetization and P31 NMR measurements under high pressure up to 6.4 GPa on RbMoOPO4Cl, which is a frustrated square-lattice antiferromagnet with competing nearest-neighbor and next-nearest-neighbor interactions. Anomalies in the pressure dependencies of the NMR shift and the transferred hyperfine coupling constants indicate a structural phase transition at 2.6 GPa, which is likely to break mirror symmetry and triggers significant change of the exchange interactions. In fact, the NMR spectra in magnetically ordered states reveal a change from the columnar antiferromagnetic (CAF) order below 3.3 GPa to the Néel antiferromagnetic (NAF) order above 3.9 GPa. The spin lattice relaxation rate 1/T1 also indicates a change of dominant magnetic fluctuations from CAF-type to NAF-type with pressure. Although the NMR spectra in the intermediate pressure region between 3.3 and 3.9 GPa show coexistence of the CAF and NAF phases, a certain component of 1/T1 shows paramagnetic behavior with persistent spin fluctuations, leaving a possibility for a quantum disordered phase. The easy-plane anisotropy of spin fluctuations with unusual nonmonotonic temperature dependence at ambient pressure gets reversed to the Ising anisotropy at high pressures. This unexpected anisotropic behavior for a spin 1/2 system may be ascribed to the strong spin-orbit coupling of Mo-4d electrons.
Article
We report the crystal structures and magnetic properties of two pseudopolymorphs of the S=1/2 Ti3+ coordination framework, KTi(C2O4)2·xH2O. Single-crystal x-ray and powder neutron diffraction measurements on α−KTi(C2O4)2·xH2O confirm its structure in the tetragonal I4/mcm space group with a square planar arrangement of Ti3+ ions. Magnetometry and specific heat measurements reveal weak antiferromagnetic interactions, with J1≈7 K and J2/J1=0.11 indicating a slight frustration of nearest- and next-nearest-neighbor interactions. Below 1.8 K, α−KTi(C2O4)2·xH2O undergoes a transition to G-type antiferromagnetic order with magnetic moments aligned along the c axis of the tetragonal structure. The estimated ordered moment of Ti3+ in α−KTi(C2O4)2·xH2O is suppressed from its spin-only value to 0.62(3)μB, thus verifying the two-dimensional nature of the magnetic interactions within the system. β−KTi(C2O4)2·2H2O, on the other hand, realizes a three-dimensional diamondlike magnetic network of Ti3+ moments within a hexagonal P6222 structure. An antiferromagnetic exchange coupling of J≈54 K—an order of magnitude larger than in α−KTi(C2O4)2·xH2O—is extracted from magnetometry and specific heat data. β−KTi(C2O4)2·2H2O undergoes Néel ordering at TN=28 K, with the magnetic moments aligned within the ab plane and a slightly reduced ordered moment of 0.79μB per Ti3+. Through density-functional theory calculations, we address the origin of the large difference in the exchange parameters between the α and β pseudopolymorphs. Given their observed magnetic behaviors, we propose α−KTi(C2O4)2·xH2O and β−KTi(C2O4)2·2H2O as close to ideal model S=1/2 Heisenberg square and diamond lattice antiferromagnets, respectively.
Article
We report magnetic properties of a 3d9 (Cu2+) magnetic insulator Cu2OSO4 measured on both powder and single crystal. The magnetic atoms of this compound form layers whose geometry can be described either as a system of chains coupled through dimers or as a kagome lattice where every third spin is replaced by a dimer. Specific heat and DC susceptibility show a magnetic transition at 20 K, which is also confirmed by neutron scattering. Magnetic entropy extracted from the specific heat data is consistent with an S=1/2 degree of freedom per Cu2+, and so is the effective moment extracted from DC susceptibility. The ground state has been identified by means of neutron diffraction on both powder and single crystal and corresponds to an ∼120∘ spin structure in which ferromagnetic intradimer alignment results in a net ferrimagnetic moment. No evidence is found for a change in lattice symmetry down to 2 K. Our results suggest that Cu2OSO4 represents a type of model lattice with frustrated interactions where interplay between magnetic order, thermal and quantum fluctuations can be explored.
Article
The magnetic and structural properties of polycrystalline Co4−xNixNb2O9 (x=1,2) have been investigated by neutron powder diffraction, magnetization and heat capacity measurements, and density functional theory (DFT) calculations. For x=1, the compound crystallizes in the trigonal P3¯c1 space group. Below TN=31 K it develops a weakly noncollinear antiferromagnetic structure with magnetic moments in the ab plane. The compound with x=2 has crystal structure of the orthorhombic Pbcn space group and shows a hard ferrimagnetic behavior below TC=47 K. For this compound a weakly noncollinear ferrimagnetic structure with two possible configurations in the ab plane was derived from neutron diffraction study. By calculating magnetic anisotropy energy via DFT, the ground-state magnetic configuration was determined for this compound. The heat capacity study in magnetic fields up to 140 kOe provides further information on the magnetic structure of the compounds.
Article
We investigated the electronic and magnetic properties of the tetragonal molybdenum phosphate MoOPO4 by means of first-principles calculations based on the density functional theory within the semilocal generalized gradient approximation that includes the Hubbard repulsion term to take into account the electronic correlations. Furthermore, the spin-orbit coupling is explored through noncollinear magnetic calculations. Our results demonstrated that the Néel ordering on the square lattice plane, experimentally observed, is indeed the magnetic ground state on condition that the effective electronic correlation correction is smaller than 2.0 eV. Otherwise, the ferromagnetic alignment is established. In addition, the out-of-plane ferromagnetic interaction is well reproduced. The computed exchange constants, extracted from the classical Heisenberg model, show that the modest antiferromagnetic in-plane nearest-neighbor coupling plays a decisive role in the stabilization of the Néel spin alignment, in conjunction with the remarkable ferromagnetic in-plane next nearest-neighbor interaction. Moreover, the sign and relative amplitude of the exchange coupling parameters is sensitive to the correlation strength we applied. The density of states and spin density analysis demonstrated that the exclusively occupied dxy orbital results in the pure S = 1/2 spin moment and negligible spin-orbit coupling, which is originated from the large displacement of Mo ions inside the MoO6 octahedra along the apical direction.
Article
Full-text available
High-resolution resonant inelastic X-ray scattering (RIXS) at the oxygen K-edge has been used to study the orbital excitations of Ca2RuO4 and Sr2RuO4. In combination with linear dichroism X-ray absorption spectroscopy, the ruthenium 4d-orbital occupation and excitations were probed through their hybridization with the oxygen p-orbitals. These results are described within a minimal model, taking into account crystal field splitting and a spin-orbit coupling \lambda_{so}=200~meV. The effects of spin-orbit interaction on the electronic structure and implications for the Mott and superconducting ground states of (Ca,Sr)2RuO4 are discussed.
Article
Full-text available
The square-lattice quantum Heisenberg antiferromagnet displays a pronounced anomaly of unknown origin in its magnetic excitation spectrum. The anomaly manifests itself only for short wavelength excitations propagating along the direction connecting nearest neighbors. Using polarized neutron spectroscopy, we have fully characterized the magnetic fluctuations in the model metal-organic compound CFTD, revealing an isotropic continuum at the anomaly indicative of fractional excitations. A theoretical framework based on the Gutzwiller projection method is developed to explain the origin of the continuum at the anomaly. This indicates that the anomaly arises from deconfined fractional spin-1/2 quasiparticle pairs, the 2D analog of 1D spinons. Away from the anomaly the conventional spin-wave spectrum is recovered as pairs of fractional quasiparticles bind to form spin-1 magnons. Our results therefore establish the existence of fractional quasiparticles in the simplest model two dimensional antiferromagnet even in the absence of frustration.
Article
Full-text available
We present new magnetic heat capacity and neutron scattering results for two magnetically frustrated molybdate pyrochlores: $S=1$ oxide Lu$_2$Mo$_2$O$_7$ and $S={\frac{1}{2}}$ oxynitride Lu$_2$Mo$_2$O$_5$N$_2$. Lu$_2$Mo$_2$O$_7$ undergoes a transition to an unconventional spin glass ground state at $T_f {\sim} 16$ K. However, the preparation of the corresponding oxynitride tunes the nature of the ground state from spin glass to quantum spin liquid. The comparison of the static and dynamic spin correlations within the oxide and oxynitride phases presented here reveals the crucial role played by quantum fluctuations in the selection of a ground state. Furthermore, we estimate an upper limit for a gap in the spin excitation spectrum of the quantum spin liquid state of the oxynitride of ${\Delta} {\sim} 0.05$ meV or ${\frac{\Delta}{|\theta|}}\sim0.004$, in units of its antiferromagnetic Weiss constant ${\theta} {\sim}-121$ K.
Article
Magnetic properties of AMoOPO4Cl (A=K,Rb) with Mo5+ ions in the 4d1 electronic configuration are investigated by magnetization, heat capacity, and nuclear magnetic resonance (NMR) measurements on single crystals, combined with powder neutron diffraction experiments. The magnetization measurements reveal that they are good model compounds for the spin-1/2J1−J2 square-lattice magnet with the first and second nearest-neighbor interactions. Magnetic transitions are observed at around 6 and 8 K in the K and Rb compounds, respectively. In contrast to the normal Néel-type antiferromagnetic order, the NMR and neutron diffraction experiments find a columnar antiferromagnetic order for each compound, which is stabilized by a dominant antiferromagnetic J2. Both compounds realize the unusual case of two interpenetrating J2 square lattices weakly coupled to each other by J1.
Article
Sr$_2$CuTeO$_6$ presents an opportunity for exploring low-dimensional magnetism on a square lattice of $S=1/2$ Cu$^{2+}$ ions. We employ ab initio multi-reference configuration interaction calculations to unravel the Cu$^{2+}$ electronic structure and to evaluate exchange interactions in Sr$_2$CuTeO$_6$. The latter results are validated by inelastic neutron scattering using linear spin-wave theory and series-expansion corrections for quantum effects to extract true coupling parameters. Using this methodology, which is quite general, we demonstrate that Sr$_2$CuTeO$_6$ is an almost realization of a nearest-neighbor Heisenberg antiferromagnet but with relatively weak coupling of 7.18(5) meV.
Book
Describing all aspects of the physics of transition metal compounds, this book provides a comprehensive overview of this unique and diverse class of solids. Beginning with the basic concepts of the physics of strongly correlated electron systems, the structure of transition metal ions, and the behaviours of transition metal ions in crystals, it goes on to cover more advanced topics such as metal-insulator transitions, orbital ordering, and novel phenomena such as multiferroics, systems with oxygen holes, and high-Tc superconductivity. Each chapter concludes with a summary of key facts and concepts, presenting all the most important information in a consistent and concise manner. Set within a modern conceptual framework, and providing a complete treatment of the fundamental factors and mechanisms that determine the properties of transition metal compounds, this is an invaluable resource for graduate students, researchers and industrial practitioners in solid state physics and chemistry, materials science, and inorganic chemistry.
Article
The electronic structure of the low-dimensional 4d(5) oxides Sr2RhO4 and Ca3CoRhO6 is herein investigated by embedded-cluster quantum chemistry calculations. A negative tetragonal-like t2g splitting is computed in Sr2RhO4 and a negative trigonal-like splitting is predicted for Ca3CoRhO6, in spite of having positive tetragonal distortions in the former material and cubic oxygen octahedra in the latter. Our findings bring to the foreground the role of longer-range crystalline anisotropy in generating noncubic potentials that compete with local distortions of the ligand cage, an issue not addressed in standard textbooks on crystal-field theory. We also show that sizable t2g(5)-t2g(4)eg(1) couplings via spin-orbit interactions produce in Sr2RhO4 [Formula: see text] ground-state expectation values significantly larger than 1, quite similar to theoretical and experimental data for 5d(5) spin-orbit-driven oxides such as Sr2IrO4. On the other hand, in Ca3CoRhO6, the [Formula: see text] values are lower because of larger t2g-eg splittings. Future X-ray magnetic circular dichroism experiments on these 4d oxides will constitute a direct test for the [Formula: see text] values that we predict here, the importance of many-body t2g-eg couplings mediated by spin-orbit interactions, and the role of low-symmetry fields associated with the extended surroundings.
Article
Two new pentavalent molybdenum chloromonophosphates, KMoOPO4Cl and RbMoOPO4Cl, have been synthesized. They crystallize in the p4/nmm space group with a = b = 6.4340(5) and c = 7.2715(9) Angstrom for the potassium compound and a = b = 6.4551(8) and c = 7.4612(8) Angstrom for the rubidium compound. Their original structure consists of [MoPO5Cl](infinity), layers parallel to (001), whose cohesion is ensured by K+ or Rb+ ions. The chloride ions and the alkali metal cations form a puckered rock salt layer. (C) 1998 Academic Press.
Article
MoOPO4 has been prepared and characterized by its X-ray powder diffraction pattern and spectroscopic techniques (uv-visible, EPR). Magnetic measurements show a 3D antiferromagnetic behavior below 18 K for this compound, in contrast to the isostructural α-VOSO4 which exhibits a 2D ferromagnetic behavior. The 31P NMR studies clearly show that the exchange mechanism involves the |PO4| tetrahedra.
Article
Local electronic structure defects in ionic crystals is commonly modeled using embedded cluster calculations. In this context we describe how to embed the quantum cluster (QC) in an array of point charges. Specifically, the method calculates an array of point charges that reproduces the electrostatic potential of the infinite crystal within an accuracy usually