Chemical Bonding in Metallic Rutile-type Oxides TO2

(T = Ru, Rh, Pd, Pt)

Gérard Demazeaua , Samir F. Matara , and Rainer Pöttgenb
a ICMCB – CNRS, Université Bordeaux 1, 87, Avenue du Docteur A. Schweitzer,
33608 Pessac Cedex, France
b Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30,
D-48149 Münster, Germany
Reprint requests to S. F. Matar. E-mail: [email protected]

Z. Naturforsch. 2007, 62b, 949 – 954; received April 4, 2007

Dedicated to Dr. Bernard Chevalier on the occasion of his 60 th birthday

Synthesis routes to rutile-type oxides with 4d and 5d transition elements are summarized. Trends in
electronic structure have been established through an analysis in the framework of density functional
theory presenting the band structure, the density of states and the properties of chemical bonding.
The metal-oxygen bond is found to play the major role in bonding of the system in the valence
band. Throughout the series 4d → 5d (RuO2 , RhO2 , PdO2 and PtO2 ) the crystal field analysis of the
band structure shows a lowering of eg towards t2g manifolds and a broadening of the overall density
of states. In the vicinity of the Fermi level the role of the antibonding metal-oxygen character is
investigated in the context of instability towards possible magnetic polarization, especially for RuO2 .

Key words: Oxides, RuO2 , RhO2 , PdO2 , PtO2 , Rutile-type, DFT

Introduction the electronegativity χ and the chemical hardness η .

Applying this model, one would expect metallic be-
Twenty years ago Zaanen, Sawatzky and Allen haviour for the group including RuO2 , RhO2 , PdO2
(ZSA) [1] proposed an interesting description of metal and PtO2 , considered herein. Complementing such
oxides taking into account correlation effects. Accord- models, the support of experimental findings (crystal-
ing to this description the electronic properties of ox- lography, physical data, etc.) by band theoretical in-
ides can be described in terms of the relative energies vestigations is of great relevance. For the transition
of three electronic energy levels near the Fermi level: metal 4d and 5d dioxides this appears to be partic-
(i) the energy-level of the oxygen 2p states fully oc- ularly important in order to evaluate the role of the
cupied, (ii) the energy level of the highest occupied T 4+ –O covalence. This is the object of the present
metal orbital, and (iii) the energy level of the lowest work.
unoccupied metal orbital (corresponding to the metal
conduction band). Experimental Data on T O2 Oxides
Among the many metal oxides, transition metal
dioxides represent an important family of materials Ruthenium dioxide appears in nature in the rutile-
due to their physical properties [2]. Besides CrO2 , an type structure [4] (Fig. 1). The high-pressure behaviour
important ferromagnetic material for recording tapes, of RuO2 was investigated either under static compres-
most of the transition metal dioxides are widely used sion [5] or shock compression [6]. Under static com-
in the field of catalysis. From the 3d to the 4d transi- pression a first phase transition was observed at 6 GPa
tion metal row, due to the increase of the strength of from the rutile-type to the orthorhombic CaCl2 -type
the T 4+ –O bond, the physical properties of the cor- characterized by a slight deformation of the ambient-
responding oxides are modified. Recently Matar and pressure tetragonal rutile structure. At 12 GPa a second
Campet [3] proposed the so-called ‘ χη model’ which transition from the CaCl2 -type to a modified fluorite-
allows predicting the metallic behaviour of an oxide. type structure with an increase of the cationic coordi-
It is mainly based on simple chemical criteria such as nation number {6 + 2} took place. Using shock com-

0932–0776 / 07 / 0700–0949 $ 06.00 © 2007 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com
950 G. Demazeau et al. · Chemical Bonding in T O2

thorhombic space group Pbnm confirmed the CaCl2 -

type structure, an orthorhombically distorted variant
of the rutile-type inducing different Pt–O distances
(2 × 1.989(4) and 4 × 2.003(4) Å).
The oxygen x parameter of RhO2 [8] was used
throughout this work as the only variable. All elec-
tronic structure computations are fully ab initio.

Theoretical Investigations of the Band Structures

Computational framework
Fig. 1. The rutile-type structure of the dioxides T O2 (T = Ru, Early [11, 12] and more recent [13, and ref. therein]
Rh, Pd, Pt). Transition metal and oxygen atoms are drawn theoretical studies on rutile-type oxides were carried
as black and light gray circles, respectively. The edge- and
corner-sharing T O6/3 octahedra are emphasized.
out with the aim of establishing the electronic struc-
ture vs. chemical bonding relationship. While the early
pression only the first transition close to 6 GPa was studies focused on a comparison of RuO2 with TiO2 ,
detected. VO2 , and CrO2 , herein we report a comparison within
Rhodium dioxide was first claimed by Muller and the series RuO2 , RhO2 , and PdO2 . Within the frame-
Roy using Rh2 O3 · 5H2 O as precursor and an oxy- work of the well established density functional the-
gen pressure up to 350 MPa [7]. A recent ther- ory DFT [14] we used the all electrons augmented
mogravimetric study of the resulting compound has spherical wave (ASW) method in a scalar relativis-
shown that stabilization by OH groups induces the for- tic implementation [15] due to the presence of heavy
mation of the rutile-type structure of the compound elements with Z > 50. The exchange-correlation ef-
[Rh4+ Rh3+ fects were accounted for within the generalized gra-
(1−x) x O2−x OHx ]. Subsequently, an anhydrous
high oxygen pressure synthesis was developed using dient approximation (GGA) using the parameteriza-
RhCl3 as a precursor and Na2 O2 as both oxidant and tion of Perdew, Burke and Ernzerhof [16]. In the
chloride trapping agent. A structural study has con- ASW method, the wave function is expanded in atom-
firmed that RhO2 adopts the rutile structure with Rh4+ centered augmented spherical waves, which are Han-
in a slightly distorted octahedral coordination of oxy- kel functions and numerical solutions of Schrödinger’s
gen atoms at Rh–O distances of 1.950 Å (4×) and equation, respectively, outside and inside the so-called
1.983 Å (2×) [8]. augmentation spheres. The transition metal ns, np and
Palladium dioxide with the rutile structure was (n − 1)d states, n = 5 for Ru, Rh, Pd and n = 6 for Pt
claimed by Shaplygin et al. [9]. The high-pressure and O 2s, 2p, were used for valence basis sets. Further,
preparation process used PdO as a precursor and ther- due to the open nature of the rutile structure, empty
mal decomposition of KClO3 as in situ oxygen source spheres (ES) were introduced within the atomic sphere
in a belt-type equipment (4 GPa, 950 ◦C). The repro- approximation ASA of the ASW method [15]. ES are
ducibility of such a preparative route appears to be dif- pseudo atoms with zero atomic numbers and a lim-
ficult due to the low thermal stability of PdO2 . ited valence basis set like oxygen, so that they receive
The preparation of platinum dioxide was first at- charges from neighboring atoms and allow for cova-
tempted under oxygen pressures (20 – 400 MPa) by lence within the structure. A sufficiently large num-
Muller and Roy using PtI2 as starting material [7]. As ber of k points were used to sample the irreducible
a function of temperature, two different modifications wedge of the simple tetragonal Brillouin zone for the
have been observed: α -PtO2 and β -PtO2 . The CdI2 - plot of the electronic band structure. The energy and
type structure was proposed for the α -form, but due charge differences between successive iterations were
to the poor crystallinity of this oxide, the structure converged below ∆E = 10−8 Ryd. and ∆Q = 10−8, re-
type requires confirmation. Single crystals of β -PtO2 spectively.
have been grown from elemental platinum and KClO3 To extract more information about the nature of the
mixtures under high pressures [4 GPa – 1500 ◦C] in a interactions between the atomic constituents from elec-
modified belt-type equipment [10]. The observed or- tronic structure calculations, the crystal orbital overlap
G. Demazeau et al. · Chemical Bonding in T O2 951

Fig. 2. Band structure of the rutile-type oxides T O2 (T = Ru, Rh, Pd, Pt) along major directions of the tetragonal Brillouin
zone.

population (COOP) [17] or the crystal orbital Hamilto- Brillouin zone of the simple tetragonal Bravais lattice.
nian population (COHP) [18] can be employed. Both Note that these oxides have 2 formula units per cell
approaches provide a qualitative description of the (T2 O4 ) so that one expects two sets of bands, i. e. 2 ×
bonding, nonbonding and antibonding interactions be- 2 eg , 2 × 3 t2g for the d metal and 4 × 3 p bands for
tween atoms. A slight refinement of the COHP was re- oxygen.
cently proposed in the form of the “energy of covalent The Oh -like crystal field analysis follows from the
bond” (ECOV), which combines COHP and COOP to simple counting of the bands. From the first panel
calculate quantities independent of the choice of the (RuO2 ), looking at the ZA line, one finds the four eg -
zero of potential [13]. Both COOP and ECOV give like bands by counting 4 dispersion lines from the top
similar general trends, but COOP, when defined within of the panel. The eg bands are all found above EF and
plane-wave basis sets, exaggerates the magnitude of well separated from the six t2g -like bands which are
antibonding states. In the present work the ECOV was crossed by the Fermi level. In RuO2 , the interesting
used for the chemical bonding analysis. In the plots, feature of the flat band in the close neighborhood of
negative, positive and zero ECOV magnitudes are rele- the Fermi level should be correlated with an instability
vant to bonding, antibonding and nonbonding interac- of the system when accounted for in the spin degener-
tions, respectively. ate (total spins) configuration such as the one assumed
here. This point is further discussed in the DOS sec-
Results of the Calculations and Discussion tion. The oxygen bands are within the valence band
Band structure and they can be counted to be 12 in number. Along
the 4d series (Ru, Rh, Pd) with one electron added up
Fig. 2 shows the band structures of the four metal for each step and a larger filling of the d subshell, the
oxide systems plotted along the major directions of the trend is towards a smaller energy difference between
952 G. Demazeau et al. · Chemical Bonding in T O2

Fig. 3. Site projected DOS accounting for the site multiplicity of the rutile-type dioxides T O2 (T = Ru, Rh, Pd, Pt).

the different bands (eg , t2g and p) and a lowering of contribution arising from the ES. It is sufficient to say
the eg bands which are crossed by the Fermi level for that they receive charge residues from both T and O.
T = Pd and Pt; for the latter the bands are no longer Due to the crystal orientation used in our calculations,
separated and one observes just one block of bands. the t2g and eg manifolds are inclusive of dx2 −y2 , dxz ,
This is a sign of an increased covalence of the bond- dyz , and dxy , dz2 , respectively. This approach is some-
ing upon going from RuO2 to RhO2 where eg and t2g what different from the usual procedure, but the differ-
mix together along the ZA line. From Pd to Pt, which ence is artificial since the physical concept is the same.
are isoelectronic, the trend is the same but with a larger From this one can notice that the eg states are mainly
energy window since the Pt(5d) bands are broader than responsible for the DOS within the valence band VB,
the Pd(4d) bands. i. e. they secure the bonding with oxygen (see for in-
stance the energy window from −8 to −6 eV), while
Density of states the t2g -like states are less involved in the bonding and
The site projected DOS (PDOS) accounting for site show intense peaks such as at EF . The different PDOS
multiplicity within the rutile structure, i. e. 2 metals per can be seen to mirror the observations made above with
4 oxygens, are shown in the four panels of Fig. 3, the the following trends:
energy reference along x being at the Fermi level. For (i) From the first panel showing the RuO2 plots,
the sake of clarity we do not show the small PDOS both the Ru and O PDOS run alike for the lower (at
G. Demazeau et al. · Chemical Bonding in T O2 953

ca. −8 eV) and upper part (between 2 and −6 eV) of

the panel; this points to the strong σ bonding within
the ‘T O6 ’-like octahedron. The relatively large DOS at
the Fermi level for Ru is due to the crossing of the t2g
manifold by EF (see band structure panel). Within the
Stoner mean field theory of band ferromagnetism [13],
the large DOS at EF is a sign of a magnetic instability,
and as a matter of fact spin-polarized calculations of
RuO2 point to the onset of a small but finite magnetic
moment of 0.044 µB per Ru atom and a total magneti-
zation of 0.116 µB per formula unit. Although former
theoretical studies on the electronic structure of RuO2
[11, 12] pointed to its metallic character, this is the first
proposal of weak ferromagnetism in RuO2 . This is un-
expected, because 4d elements are rarely seen to sup-
port a spontaneous magnetic moment. Nevertheless, Fig. 4. Different interactions accounting for the site multi-
plicity of the ECOV criterion for rutile-type RhO2 .
this could be changed as a result of the experimental
conditions of sample preparation (bulk, thin layers. . .) positive and zero ECOV magnitudes point to bond-
and needs to be checked experimentally. Moreover this ing, antibonding and non-bonding interactions, respec-
is not significant of a true magnetically ordered system tively. It can be observed that the major pair interac-
such as CrO2 formerly studied by us in the same the- tion within the metal oxide systems arises from metal-
oretical framework [13]. It needs to be noted here that oxygen bonding while only small contributions arise
a large DOS at the Fermi level arising from t2g -like from T –T (Rh–Rh) and O–O bonding. The T –O bond-
orbitals is correlated with a certain instability of such ing includes σ and π interactions involving the eg and
a non magnetic state. In VO2 , the system “relaxes” to t2g manifolds, respectively. This stabilizes the system
become monoclinic; this translates as a structural in- within the valence band up to −2 eV. However, at
stability. In CrO2 the system relaxes to become a half the top of the valence band antibonding states appear
metallic ferromagnet, and RuO2 seems to be on the with π ∗ bonding from t2g manifolds; this is continued
verge of such a magnetic instability. within the conduction band with σ ∗ interactions. This
(ii) Within the series of 4d compounds, the T metal scheme of bonding resembles a classical molecular or-
PDOS at EF decreases due to the energy lowering of bital (MO) diagram with σ and σ ∗ MO’s much more
the eg states until they are crossed by EF for Pd and Pt. separated, i. e. σ ∗ states higher in energy than weaker
A striking feature is the overall decrease of the DOS π and π ∗ MO’s. This is like the diagram formerly de-
intensity and the similarity of the T and O PDOS espe- scribed by Sorantin and Schwarz [12] for rutile-type
cially for Pd and Pt. This is related to the larger quan- oxides. It appears that at least part of the magnetic in-
tum mixing between T and O whereby electrons are stability of the large DOS at EF of these systems is due
exchanged between T and O. From the calculations to antibonding states.
we find that the relative O(2p) occupation is increased
from RuO2 to PdO2 and PtO2 . This charge exchange Conclusions
is in line with the increase of the covalent character of
the bond. The oxides T O2 (T = Ru, Rh, Pd, Pt) have been
prepared through different routes. While RuO2 also
Chemical bonding is found in nature, the synthesis of the other diox-
ides with T = Rh, Pd, Pt (not present in minerals) re-
To represent all four systems, the chemical bonding quires high oxygen pressures. Due to the strong co-
is illustrated in Fig. 4 using results of RhO2 , follow- valence of the T 4+ –O chemical bond with T = 4d
ing the ECOV approach which merges both the Hamil- and 5d transition metals, such dioxides are suitable
tonian Hij and the overlap Sij analyses for pair inter- candidates for theoretical investigations of their elec-
actions [19]. Along the y coordinate axis, negative, tronic band structures. First principles self consistent
954 G. Demazeau et al. · Chemical Bonding in T O2

computations providing a quantitative description of ization of Ru(4d) states within a mean field theory of
the band structure, the density of states DOS and the band ferromagnetism. The bonding within the VB is
chemical bonding characteristics can be carried out in found to be predominantly of metal-oxygen character
the framework of density functional theory. They al- with low lying σ bonding and π -like bonding at higher
low for showing trends within the series of T O2 ox- energy, followed by π ∗ and σ ∗ states in an MO like
ides: The metallic character is mainly due to d states manner.
of the transition metal with different degrees of t2g /eg
character. From energy positions of the bands and the Acknowledgements
DOS shapes the role of the metal and oxygen orbitals Calculations were carried out on the main frame com-
has been analyzed. There is an increasing rate of co- puters of the Université Bordeaux 1, M3PEC-Mésocentre
valence within the series mainly through a broadening (http://www.m3pec.u-bordeaux1.fr). This work was sup-
of the valence band (VB). A large DOS magnitude at ported by the Deutsche Forschungsgemeinschaft and the Eu-
the Fermi level was identified for the ruthenium oxide ropean Science Foundation through the COST D30 pro-
system and analyzed regarding on-site magnetic polar- gramme.

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