Ruthenium dioxide RuO2 : effect of the altermagnetism on the physical properties

Andrzej Ptok1, ∗
1
Institute of Nuclear Physics, Polish Academy of Sciences, W. E. Radzikowskiego 152, PL-31342 Kraków, Poland
(Dated: September 6, 2023)
Ruthenium oxide with the rutile structure is one of example of altermagnets. These systems are
characterized by compensated magnetic moments (typical for antiferromagnets) and strong time
reversal symmetry breaking (typical for ferromagnets). However, in such cases, the electronic band
structure exhibit strong spin splitting along some directions in the momentum space. Occurrence
of the compensated magnetic textures allows for realization of surfaces with specific magnetization,
which dependent on the surface orientation and/or its termination. Here, we study interplay between
arXiv:2309.02421v1 [cond-mat.mtrl-sci] 5 Sep 2023

the electronic surface states and the surface magnetization. We show that the spin-resolved spectra
strongly depends on a direction in reciprocal space. Such properties can be used for the experimental
confirmation of the altermagnetism in RuO2 within the spectroscopic techniques. Additionally, we
show that the most modified orbitals in the system are dz2 and dxy orbitals of Ru. Similarly, the Ru
eg states are most sensitive on epitaxial strain, what can suggest some link between altermagnetism
and strain.

I. INTRODUCTION tion of the roto-reversal symmetry [6] and compensated

antiparallel magnetic moments leads to the anomalous
In the simplest case of crystals with collinear mag- Hall effect of comparable strength as for other ferromag-
netic order, the ferromagnetic and antiferromagnetic sys- nets [7, 8]. As a consequence, the chiral magnons can
tems were considered. The ferromagnetism corresponds be realized [9], what has a potential to application in the
to the strong magnetization and to the spin-polarization novel spinotronic devices [10–13]. Additionally, this com-
in electronic bands that breaks the time reversal sym- pound exhibits several interesting features like non-trivial
metry. In contrast to this, the antiferromagnetism gen- topological properties [14–16], and superconductivity in-
erates compensated collinear order with no total mag- duced by epitaxial strain [17, 18]. Moreover, as a highly
netization. More recently, altermagnets – a third ele- conductivity binary oxide [19, 20], it could be used in
mentary class of crystal with a collinear magnetic order many engineering applications [21].
has been discovered [1, 2]. In such a case, the system Realization of the altermagnetism in RuO2 is associ-
exhibits a symmetry-protected compensated antiparallel ated with strong time-reversal symmetry breaking, which
magnetic order on a crystal lattice that generates un- is exhibited by strong mismatch between opposite spin
conventional alternating spin-polarization and the time- bands along some direction [Fig. 1(b)]. Nevertheless, in
reversal-symmetry breaking in the band structure with- real space, the system is characterized by compensated
out magnetization [3]. magnetic moments [Fig. 1(a)], what allows for a realiza-
One of compounds exhibiting the altermagnetism is tion of the surfaces terminated by Ru atoms belonging
RuO2 with the rutile structure (Fig. 1). In this material, to the same magnetic sublattice and with the same mag-
the collinear antiferromagnetic order is observed in rela- netization. Additionally, we can expect that the surface
tively high temperatures (TN > 300 K) [4, 5]. Combina- orientation can affect the physical properties of the sys-
tem. Indeed, for example, the spin orientation on the
surface affects on the thermal conductivity of the ma-
terial [22]. The role of the RuO2 surface magnetism is
also well know in the context of catalyses [23] or oxygen
evolution reaction [24]. More recently, also the strong
time-reversal symmetry breaking was observed in mag-
netic circular dichroism [25], as well as on spin-dependent
emitted light experiments [26]. However, the problem
of the interplay between altermagnetism and electronic
properties is still open, especially in the context of topo-
logical features of RuO2 -like compounds [14–16, 27], or
FIG. 1. (a) The crystal structure of RuO2 with the ru-
generally antiferromagnetic compounds [28].
tile structure. (b) The electronic band structure, showing In this paper, we discuss consequences of occurring
a strongly broken time reversal symmetry and altermagnetic altermagnetism on the surface states dependent on the
features of RuO2 . surface orientation and termination. Recent study indi-
cate that the spin-resolved spectroscopy can be used for
confirmation of the altermagnetism in MnTe [29]. In-
deed, spin splitting can affect on the spin polarization
∗ e-mail: aptok@mmj.pl of the surface states. However, mentioned MnTe mate-
 2

rial [29] is characterized by relatively small band split- 44-band model. Finally, the electronic surface states were
ting. Contrary to this, in the RuO2 band splitting is calculated using the surface Green’s function technique
around 1 eV [2] and is much larger than in other alter- for a semi-infinite system [45], implemented in Wannier-
magnets [30]. This makes RuO2 as an excellent candidate Tools [46].
for experimental study of the altermagnetism within the
spectroscopy techniques [31].
The paper is organized as follows. The computational
details are present in Sec II. Next, in Sec. III, we present
and discuss our numerical results. Finally, a summary is III. RESULTS AND DISCUSSION
included in Sec. IV.
A. Crystal structure
II. COMPUTATIONAL DETAILS
RuO2 crystallizes with the rutile structure (P42 /mnm,
The first-principles density functional theory (DFT) space group No. 136) presented in Fig. 1(a). In this case,
calculations were performed using the projector the Ru and O atoms are located in Wyckoff positions 2b
augmented-wave (PAW) potentials [32] implemented (0,0,0) and 4g (xO ,yO ,0), respectively. Here, xO and yO
in the Vienna Ab initio Simulation Package (Vasp) are two free parameters describing position of O atoms
code [33–35]. For the exchange-correlation energy in the crystal structure.
the generalized gradient approximation (GGA) in the
The obtained crystal parameters for different U are
Perdew, Burke, and Ernzerhof (PBE) parametrization
collected in Table ST1 in the Supplementary Materials
was used [36]. Similarly to the previous study, we
(SM) [47]. In practice, all lattice parameters are sim-
introduce the correlation effects on Ru d orbitals within
ilar, and only Ru magnetic moments strongly depends
DFT+U approach, introduced by Dudarev et al. [37].
by U . Similarly like in the previous study [48], we as-
The energy cutoff for the plane-wave expansion was set
sume U = 2 eV, for which Ru posses the magnetic mo-
to 600 eV. Optimization of the structural parameters (in
ment 1.152 µB . In this case, a = 4.533 Å, c = 3.11 Å,
the presence of the spin–orbit coupling) were performed
while the free parameters are obtained as xO = 0.8037
using 10 × 10 × 15 k–point grid using the Monkhorst–
and yO = 0.1963. The lattice constant are closed to
Pack scheme [38]. As a convergence condition of the
the experimentally observed ones, i.e., a = 4.49 Å, and
optimization loop, we took the energy change below
c = 3.11 Å [5].
10−6 eV and 10−8 eV for ionic and electronic degrees of
freedom.
The study of the electronic surface properties we con-
struct the tight-binding model in the maximally localized
Wannier orbitals [39–41]. In this case, the DFT calcula-
tion were performed within Quantum ESPRESSO [42].
Calculations were done on 8×8×8 k-grid, within DFT+U
scheme (like previously) and PBE PAW pseudopotentials
developed within PSlibrary [43]. Here, we take 100 Ry
and 450 Ry for wavefunctions and charge density cut-
offs, respectively. The exact band structure was used to
construct the tight-binding model by Wannier90 [44],
based on Ru d and O p orbitals, what correspond to a

FIG. 3. The strongest modified Wannier orbitals in Ruo2

FIG. 2. Realization of the roto-reversal symmetry in RuO2 altermagnet: dz2 -like and dxy -like molecular orbitals (left and
and its consequences on the spin (a) and charge (b) density right panels, respectively). Color of isosurface corresponds to
from ab initio calculations. the wave-function phase.
 3

B. Magnetic moments and spin–orbit coupling

RuO2 contains two sublattices with different Ru mag-

netic moment orientation [see Fig. 1(a)]. A relation be-
tween these two sublattices is described by the screw four-
folded rotational symmetry {4+ 111
001 | 2 2 2 } around z axis,
which is one of space group P42 /mnm generators. This
generator acting on the one Ru sublattice transforms it
to the second sublattice with opposite Ru magnetic mo-
ments [see Fig. 2(a)]. Moreover, this symmetry is also
“inherited” by the spin/charge density. This is related
to the relation between Ru d orbitals in both sublattices
given by the mentioned space group generator. Indeed,
the direct calculations of the spin and charge densities
within ab initio exhibit the same features (see Fig. 2).
However, analyses of the Wannier orbitals realized in the FIG. 5. The Fermi surface of RuO2 in the presence of spin–
system reveals that the strongest modified orbitals have orbit coupling. Top panels (a) present the full Fermi surface,
form of dz2 -like and dxy -like orbitals (Fig. 3). while bottom panels (b)–(e) present the separate Fermi pock-
ets.
There is also well-know sensitivity of RuO2 on epitax-
ial strain [17, 18], which can induce the superconductivity
in this compound. To check this behaviour, we introduce gest a link between epitaxial strain and altermagnetism.
the intentional modification of a = b lattice constants,
The magnetic moments on Ru atoms exhibit an ordi-
and found corresponding c lattice parameter, which min-
nary anitferromagnetic order [Fig. 1(a)]. However, di-
imize the system energy (see Fig. SF3 in SM [47]). This
rection of the magnetic moments on Ru is still under
should lead to mimic the effect of epitaxial strain, due
debate [50]. In our calculations, the system energy is
to the mismatch between such modified RuO2 and based
minimized when the Ru magnetic moments are parallel
material in ab plane. For this fixed parameters, we ob-
to c axis. Additionally, the value of Ru magnetic moment
tain electronic density of states. The electronic density of
weakly depends on a assumed direction and it changes in
states analyses reveals strongly sensitive Ru eg orbitals
range of 1 µB (for U = 2 eV). Moreover, the magnetic
on the epitaxial strain, what is in an agreement with the
moment direction has negligible impact on the electronic
previous study [49]. This is interesting in the context of
band structure [cf. Fig. 4 and Fig. SF2 in SM [47]]. As
the molecular orbitals realized in RuO2 . The strongest
a consequence of the changed magnetic moment direc-
modified Ru d orbitals take form of dz2 -like and dxy -like
tion, only additional tiny (invisible on the figures) band
orbitals (Fig. 3), even if the band crossing at the Fermi
splitting appears.
level have Ru dxz and dyz character [30]. This can sug-
The electronic band structure in the absence of the
spin–orbit coupling is presented on Fig. 1(b). The spin-
splitting of the band observed along two perpendicular
Γ–M paths exhibits alternating structure (cf. red and
blue color bands). Due to the crystal symmetry, each Ru
atoms is located inside octahedrons formed by O atoms.
As a consequence, the band splitting originate only from
the different magnetic moments in Ru sublattices. As

FIG. 4. Electronic band structure of RuO2 in the absence

and in the presence of the spin–orbit coupling (orange and FIG. 6. Spin polarization of the bulk Fermi surface (a,b) for
blue lines, respectively). two different cross-section of the Brillouin zone (c).
 4

FIG. 7. Spectral function (left column) and spin polarization (right column) of the states for (001) surface, terminated by Ru
atoms with ↑ and ↓ magnetic moments (upper and lower row, respectively). Here, M̄ = ( 12 12 ) and M̄ ′ = (− 12 12 ).

we can see, the band splitting is around 1 eV. Introduc- C. Spin polarization of bulk and surface states
tion of the spin–orbit coupling leads to opening a gap at
the place of the band crossing (Fig. 4). The spin–orbit
Independently from the spin–orbit coupling, the band
strength is the biggest one on Ru atoms (around 3 meV
possess strong spin polarization. Indeed, this is well vis-
and 11 meV for p and d orbitals, respectively), whereas
ible within the spin polarization analyses of the Fermi
for O atoms is negligible small (around 0.05 meV for p or-
surface. In Fig. 6, we present average projection of spin
bitals). The magnetic anisotropy energy (MAE) between
on z axis (⟨sz ⟩). In the case of Γ–X–M plane (kz = 0),
states with magnetic moment along c and a is around
the inner Fermi pockets (around Γ point) are character-
0.6 meV/f.u.
ized by d − wave spin–momentum locking [1]. In the
case of the outer Fermi pockets (around M point,) the
The spin–orbit coupling affects also on the Fermi sur- spin–momentum locking can be more complicated.
fce states. In the absence of the spin–orbit coupling, Bands avoiding crossing, due to the gap induced by
the Fermi surface presented on Fig. SF1 in SM [47] ex- the spin–orbit coupling, lead to existence of the sepa-
hibits a toroidal-like deformation [51] due to the symmet- rable Fermi pockets (see Fig. 5). The gap induced by
ric spin splitting [52]. The gap induced by the spin–orbit the spin–orbit coupling plays important role for occur-
coupling plays a crucial role on the Fermi surface shape rence of the topological properties. This can be shown
[Fig. 5(a)]. In this case, the Fermi surface is constructed by the Berry curvature Ω(k) calculations [3, 22]. The
by four Fermi pockets [Fig. 5(b)–(e)] with three dimen- non-vanishing integrated Berry curvature gives rise to
sional character. the intrinsic Hall conductivity. Nevertheless, even for
specific Fermi pocket, the spin polarization of the Fermi
As we know, the strength of the spin–orbit coupling surface changes significantly (i.e. spin-up ⇄ spin-down,
strongly depends on the atomic mass [53]. RuO2 is com- under rotation around z direction). This means that the
posed by relatively light atoms, however, the modifica- nodal lines of the spin polarization (i.e., ⟨sz ⟩ = 0) can be
tion of the electronic band structure and the Fermi sur- found.
face by the relativistic effect in the frame of spin–orbit That strong spin polarization of the bulk states can
coupling cannot be neglected. be reflected also within the spin polarization of sur-
 5

larization possesses the opposite spin polarization. Sim-

ilarly, the spin polarization of the Fermi surface states
within the constant energy contour measurement should
be related to the bulk polarization presented in Fig. 6.
These features should be possible to measure in a rela-
tively simple way within the spin-polarized spectroscopic
techniques [31].
IV. SUMMARY

Confirmation of the time-reversal symmetry break-

ing [25] and altermagnetism [29] is a new challenge nowa-
FIG. 8. The same as Fig. 7, but for (100) surface terminated days. In this paper, we discussed the effect of the al-
by Ru with ↓ magnetic moment. Here R̄ = ( 12 21 ), and R̄′ = termagnetism on the physical properties of ruthenium
(− 12 12 ). dioxide RuO2 , in the context of the spin-resolved spec-
troscopy.
First of all, we discussed the basic properties of the
face states. In similar way as above, using semi-infinite system, claiming that the most modified Wannier or-
method, we can calculate the spin polarization of the bitals are Ru dz2 and dxy orbitals what is in contrary
surface states as: to the previous study. Additionally, we show that the

Ru eg orbitals are very sensitive to the epitaxial strain,

1 σz Gs k∥ , ω + iη what can also suggest a link between strain and the alter-
⟨sz ⟩ k∥ , ω = − lim
, (1) magnetism. We showed a negligible role of the magnetic
π η→0+ A k∥ , ω
moments orientation on the electronic band structure.
where G denotes surface Green function, while A is sur- Finally, we focused also on the spin-resolved spectro-
face spectral function for energy ω and k is parallel to the scopic evidence of the spin-polarized (bulk and surface)
surface. In our analyses, we present results for (001) and states. RuO2 is characterized by relatively large band
(100) surfaces (Fig. 7 and 8, respectively). For such sur- spin splitting, what makes this compound excellent can-
faces, the termination is realized by the Ru atoms from didate to the altermagnetism study within spectroscopic
the same magnetic sublattice. Contrary to this, the (111) techniques. The spin-splitting has a crucial role on the
surface is terminated by Ru atoms from both sublattices surface orientation with termination by the Ru atoms
and presented analyses have no application to this sur- from one magnetic sublattice. We showed that the sur-
face. face states in such case [e.g., (001) or (100) surfaces for
First of all, we should notice, that the (001) and RuO2 ] are characterized by the absence of the symmetry
(100) surfaces posses the two-folded rotational symme- in spin-polarized spectra along some directions. This can
try (around normal vector n̂ to the surface), what is re- be used as a experimental evidence of the altermagnetism
lated with environment of Ru atoms. This is reflected in the compounds with large bands spin-splitting.
in the form of ordinary surface states along Γ̄–M̄ [for
(001)] or Γ̄–R̄ [for (100)], presented in the central part of
Fig. 7(a,b) and Fig. 8(a), respectively. In such cases, the ACKNOWLEDGMENTS
surface spectrum function does not possess the symme-
try with respect to the two–folded rotational symmetry The author thanks Konrad J. Kapcia for helpful dis-
around n̂. Contrary to this, another directions, like Γ–X̄ cussions and critical reading of the manuscript. Some
and X̄–M̄ for (001), do not exhibit these features. Such figures in this work were rendered using Vesta [54] and
absence of the surface states symmetry is also reflected XCrySDen [55] software. A.P. is grateful to Labora-
in the spin polarization [see Fig. 7(c,d) and Fig. 8(b)]. toire de Physique des Solides in Orsay (CNRS, Univer-
The projection of the strongly spin polarized bulk state sity Paris Saclay) for hospitality during a part of the
on the two dimensional surface Brillouin zone leads to work on this project. We kindly acknowledge support by
arise the spin polarized surface states. As we can see, de- National Science Centre (NCN, Poland) under Project
pending on the direction of measurements, the spin po- No. 2021/43/B/ST3/02166.

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 1

Supplemental Material
Ruthenium dioxide RuO2 : effect of the altermagnetism on the physical properties
Andrzej Ptok
(Dated: September 6, 2023)

In this Supplemental Material, we present additional results:

• Table ST1 – The optimized lattice parameters within DFT+U scheme (lattice constants, Ru magnetic moments,
and lattice free parameters describing O atoms positions).
• Figure SF1 – The Fermi surfaces for spin-↑ and spin-↓ electrons (in the absence of the spin–orbit coupling).
• Figure SF2 – The electronic band structures for Ru magnetic moments tilted from c direction.
• Figure SF3 – Role of the epitaxial strain on the electronic density of states.

TABLE ST1. Lattice parameters of RuO2 after optimization for different Hubbard-U parameters. Experimentally reported
values are: a = 4.49 Å, and c = 3.11 Å [5].

U (eV) a (Å) c (Å) MRu (µB ) xO yO

0.0 4.522 3.119 0.000 0.8057 0.1943
0.5 4.518 3.119 0.025 0.8054 0.1946
1.0 4.516 3.120 0.062 0.8043 0.1957
1.5 4.524 3.123 0.928 0.8037 0.1963
2.0 4.533 3.124 1.169 0.8037 0.1963
2.5 4.541 3.123 1.338 0.8039 0.1961
3.0 4.544 3.123 1.442 0.8041 0.1959
3.5 4.545 3.123 1.516 0.8042 0.1958
4.0 4.544 3.122 1.580 0.8044 0.1956

FIG. SF1. Top and overall view of the Fermi surface of RuO2 (top and bottom panels, respectively) in the absence of spin–orbit
coupling. Results for spin-↑ (a) and spin-↓ (b) chanels.
 2

FIG. SF2. Electronic band structure of RuO2 in the absence and in the presence of the spin–orbit coupling (orange and blue
lines, respectively). Results for M ∥ (101) (a) and M ∥ (111) (b).

FIG. SF3. Influence of the epitaxial strain on RuO2 (in the absence of the spin–orbit coupling). For fixed a lattice constant
(red, green, and blue lines), we find c lattice parameter dependence of the system energy (a). The optimized c value can be
found as the minimum of the system energy (marked by solid arrows). Densities of states (DOS) for such optimized c lattice
parameters for different fixed a lattice parameters (b)-(d). Black line corresponds to the total DOS, while red and blue lines
present partial DOSs related to Ru t2g and Ru eg states. Blue solid arrows present positions of the peaks related to Ru eg
states.