Transition Metal Oxides:
Geometric and Electronic Structures
Introducing Solid State Topics in lnorganic Chemistry Courses
Adela Muiioz-Paez
Departamento de Quimica Inorganica, Facultad de Quimica, Universidad de Sevilla, Apdo, 553,41012 Sevilla, Spain
The Study of lnorganic Solids
Although transition metal oxides have been known for a
long time, in the last decade there has been a n increasing
interest in them due to their important role in heteroge-
neous catalysis (1)and more recently in material science,
where high temperature superconductors have attracted
much attention among research groups from all over the
world (2).When studying any group of compounds the first
questions asked concern the geometric and electronic
structures because these determine their physical proper-
ties and reactivity. For transition metal oxides much infor-
mation is available on geometric structure.
Diversity in Structure
Upon examining this information, a wide variety of geo-
metric arrangements are found, including
three-dimensional
layered
chain
molecular
This variety produces a wide range in the values of cer-
tain physical properties, such as
melting points from 2800 'C for HfOz to 6 'C for MnzO7
color, including the entire spectrum
electrical pmperties, fmm insulators (CrO)
to metallic conductors (TiO)
Nevertheless, most of the oxides fall in the first group of
structures: the infinite three-dimensional. Thus, they are
usually high melting point solids. The last three classes
form a negligible fraction of all oxides.
Information about the electronic structure of is scarce
and can lead to different and often contradictory conclu-
sions, depending on the source. The reason for this lack of
information is the special difficulty encoutered in studying
the bonds in these compounds. Although most are solids a t
room temperature, they do not fit the ionic model well, nor
can they be included among the compounds that form infi-
nite covalent networks. Moreover, some properties of these
compounds show values close to those of metals, for exam-
ple, the electrical conductivities of Ti0 and VO.
Increased Interest and Use
My main purpose for this presentation is the growing
value of studying the solid state in inorganic chemistry.
The importance of solid state materials in everyday life is
reflected in the increasing use of such compounds in diode
lasers, semiconductors, or liquid crystals. The preparation
and characterization of many of these compounds has been
carried out by chemists. Consequently, the ACS Division of
Inorganic Chemistry has developed an integrated set ofin-
structional materials in solid state chemistry.
Additionally, segments of this topic have begun appear-
ing in inorganic chemistry textbooks (351. In the same
trend, solid state chemistry is the subject of several papers
that have recently appeared in this Journal (6-8). Even a
movement to introduce topics in solid state chemistry in
the laboratories has been reported (9).
Pedagogical Value of Focusing on These Metal Oxides
Transition metal oxides have been selected to achieve
this goal for several reasons.
'Agood organizingprinciple is involved: They are binaryeom-
binations of oxygen and elements fmm the transition series.
T h i s emu0 of com~ounds eonvenientlvillustrates the varietv
and &m&xity df crystalline struckres possible for inor-
ganic solids.
'These compounds provide a good way of introducing bond
theories in solid state chemistry.
Unfortunately, chemistry curricula are oRen restricted to
the study of bonding in molecular compounds. A serious
approach to the study of the electronic structure of inor-
ganic solids thus challenges the student withuew theories.
I have divided this paper into two parts. First I deal with
geometric structures and offer a summarized description
of the crystal structures that appear most otten in these
compounds. Because this is intended as only an introduc-
tion to the studv of transition metal oxides., onlv " bulk
structures of stoichiometric compounds will be examined,
thus excluding surface and defective structures. which are
by themselvesanother wide topic. The main s o k e s of in-
formation for this part are the textbooks from Wells (101,
Kung (I), Gutierrez Rios (Il), and Shriver et al. (3).
The second half of this uauer is devoted to the studv of
the electronic structure ofthi oxides and includes a reAew
of bond theories currently amlied in the field. This section
is thus more subjective andopen to discussion. The books
used to prepare it are by Phillips and Williams (121, Cox
(131, Duffy (141, Ziman (151, and West (16).
A similar version of this presentation (except for the part
dealing with the Hubbard model) has been used with un-
dergraduate students who had previously completed
coursework on bonding and crystallography. As a comple-
mentary work in the laboratory, the preparation of Y-Ba-
Cu superconductors is proposed as well as the study of the
Meissner effect. This complex oxide has been chosen be-
cause it is one of the most famous compounds involving
transition metal oxides. Also, its preparation involves solid
state techniques easily available in inorganic chemistry
laboratories (171, and the degree of success is easily
checked using the Meisnner effect.
Determinants of Geometric Structure
An examination of the known structures of binary ox-
ides. summarized in Table 1 (1). . .. shows that transition
metal oxides exist in many different crystal forms. The
classification used in Table 1was chosen to show schemat-
ically all the types of structures that appear in these ox-
ides. The oxides are arranged horizontally, as in the peri-
Volume 71 Number 5 May 1994 381
 Table 1. Crystal Structures of Some Common Transition Metal Oxides

cris
Monoxides Ti0 VO MnO FeO COO NiO CuO ZnO
NaCl NaCl NaCl NaCl NaCl NaCl RS W
Sesquioxides SC203 Ti203 v203 Crz03 Mn203 Fez03
c cor wr COT c cor, sp
Dioxides Ti02 VOz Cr02 MnOz
rut a,b rut, mono rut rut, mt
Pentoxides Spinels Vz05 Mn304 Fe304 Co304
I SP SP cor, sp
Trioxides Heptoxides Cra MnnO7
or mol
Monoxides ZrO NbO PdO AgzO CdO
NaCl RS cris NaCl
Sesquioxides Yz03 Rhz03
c cor
Dioxides ZrOz NbOz Moon Tc02 Ru02 RhOn
f, mono, let rut rut rut mt rut
Pentoxides Nbz05
or
Trioxides Heptoxides Moos TC207
I, or or
Tetroxides Ru04
mol
Monoxides La203 HgO
Sesquioxides mt or
Dioxides HfOz Ta02 W02 Re02 OsO2 Ira ROZ
f, mono, tet rut rut mono, rut rut ~t rut
Pentoxides Spinels Taz05 %304
or cub
Trioxides W03 Re03
Ephases cub
Heptoxides Tetroxides Re& 0504
or mol
.
cris = cristobaiite.NaCl = rock sat, W= wurtzile. C = C-M203.C O =~ corundum. SP =spinel.rui = rutile, a = anatase,b = bmoldte, mono = monoclinic,mt = multiple.
I = layer, or = ortharhombic, mol = molecular, f = fluofie, tet = tetragonal, cub = cubic

odic table, by increasing atomic number of the transition
metal. Within a group the oxides are arranged vertically by
increasing oxidation state of the metal as you go down the
column.
Oxidation States
In the first transition metal series, oxidation states
range from one to seven, in the second from one to eight,
d two to eight. The only oxides formed
and in the t ~ r from
by group 3 metals (Sc, Y, and La) are the sesquioxides
Mz03,whereas for gmup 12 metals (Zn, Cd, and Hg) only
the monoxides are stable under normal conditions. In the
intermediate groups, higher oxidation states are stable.
Consequently, the number of oxides from each element in-
creases, with the maximum occurring in group 7 (Mn, Tc,
and Re).
Simple a n d Complex Formulas
This table includes oxides with simple formulas, such as
Mz0, MO, MpOs, in which the metal occurs in only one ox-
idation state. I t also shows oxides of the formula M30a,
which contains both M%and M3+.There are numerous ex-
amples of more complex stoichiometric oxides that also
contain the metal in two oxidation states, for example,
MnsOs, Vs013, and Cr5012.Moreover, some metals form ex-
tensive series of oxides, such as Ti,Oz. _ lor Monos,_ with
structures related to simple oxides, MOzor M03.
Polymorphism and Packing
The organization of Table 1shows the diversity of struc-
tures. which a t first does not seem to follow anv svstematic
trend. I t also highlights the polymorphism, w&cdis partic-
ularly frequent in dioxides. Althoueh -
- each eeometric struc-
ture is stable for a given temperature range, the coexist-
ence of several crystalline ~ h a s e sis still ~ossiblefor a
given compound a; mom temperature: The Bctivation en-
ergy is hiah for the transformation from the less thermodv-
nLmically stable structure to the more stable one.
For transition metal oxides only one generalization can
be made: The ionic radius of a transition metal is usually
smaller than that of 0%.Thus, the oxide structures usu-
ally show cubic close packing of anions, with the smaller
metal cations situated in the octahedral and tetrahedral
holes of the oxide network.
Typical Three-Dimensional Structures
A detailed description of structures grouped according to
the different atoichiometries follows. Most of the struc-
tures included in Table 1are common in other types of sol-

382 Journal of Chemical Education

 Table 2. Crystalllne Structures for MO Table 3. Crystalllne Structures for M02 (Rutile Type)
(Rock Salt Type)

Transition4 5 6 7 8 9 10 11 12
Cr Mn'
Series
first Ti V Mn Fe Co Ni cub Zna
& V^
Nb
Ta
Mo
W
Tc
Re'
Ru
0s
Rh
lr Ft
second Zr NbC pdb Cd 'Polvmomhic
'~doptsfiuo"tetype rather than rutile-typestructure.
third HgC
'Assumes wultzie structure.
bAssumesPIS structure. Fluorite and Rutile
'Assumes other structures.
Most transition metal dioxides crystallize with one of the
two simple structures-flourite and rutile--shown in Fig-
ids (e.g., rock salt, rutile, and flourite), so no detailed de- ure 2.The larger MQcations Zr and Hf are octaeoordinated
scription of them will be given here. i n the flourite structure, and the smaller are hexa-
coordinated in the rutile strudwe.
Monoxides MO
Monoxides are known for all elements in the first transi-
tion metal series except scandium and chromium. Monox-
ides are also formed by some elements of the second series
(Zr, Nb,Pd, and Cd), as well as Hg in the third. Their crys-
tal structures are summarized in Table 2 and drawn in
Figure 1. FLUORITE RUTILE
Figure 2. C!ystal structures of fluorite and rutile (a metal cations, 0
oxide anions).

In the normal rutile form, each M4+is equidistant from

Figure 1. Crystal structures of rock san. FtS, and wurtziie (0 metal
cations, 0 oxide anions).
Rock Salt, Wurtzite, and PtS
Most transition metal monoxides adopt rock salt struc-
ture. Oxides can also adopt other structures, including
wurtzite (adopted by ZnO) and PtS structure (adopted by
CuO and PdO). This structure implies square planar coor-
dination around the metal cation. NhO is unique, having a
structure in which both Nb and 0 form four coplanar
bonds. occuovine alternate oositions in one of the sirnolest
3 ~ - c o ~ n e c i enets.
h ~ l t e ~ a t i v cthe
l ~ structure
, is de-
scribed as a defect NaCl structure having three h'bO in the
unit cell.
Distorted Structures and Nonstoichiometrie Forms
The classification described in Table 1implies only that
the structure of a particular compound is of the general
type indicated, and not necessarily the ideal structure with
maximum symmetry. Thus, for a given oxide, less symmet-
ric structures in which the atoms slightly deviate from the
ideal positions can be found.
Additionally, the existence of anionic and cationicvacan-
cies can be observed in some oxides, thus leading to the
formation of nonstoichiometric compounds, for example,
monoxides of Mn and Fe. Moreover, Ti, V, and Nb monox-
ides show appreciable ranges of composition, keeping the
same type of unit cell but changing the dimensions of it.
two others in each chain of octahedra. Dioxides of V,Nh,
Mo. Tc. W. and Re crvstallize with less svmmetrical vari-
ant's of this structwt?, showing successive pairs of metal
atoms alwrnativelv closer torrether and further aDart. The
close approach of metal atoms has been related td the high
electrical conductivity shown by these compounds.
Polymorphism
As shown in Table 3, polymorphism is very common in
this group of oxides. For example, Ti and Zr dioxides are
trimorphic a t atmospheric pressure. Titanium dioxide
crystallizes in rutile structure above 700 'C in which the
coordination group around the metal ion closely appmxi-
mates a regular octahedron. It also crystallizes in the less
symmetric anatase a t room temperature and in brookite
for higher pressures. In ZrOz the normal monoclinic form
changes at about 1100 'C to a tetragonal form and a t about
2300 'C to a flourite form.
SesquioxidesMZOJ
This stoichiometry is the last one appearing in a wide
group of elements. As shown in Table 4, sesquioxides are
formed by the metals in the first transition series up to
iron, by yttrium and rhodium in the second, and by lantha-
num in the third.
Corundum and C-Mz03
Crystal structures adopted by these compounds are co-
rundum and type C-Mz03.Corundum can be described as
Table 4. Transition Elements That Form
Sesquioxides M203 (Corundum Type)

Dioxides MOz
~a~
Many elements from the transition series form dioxides, 'Assumes C-Mz03 structure.
as indicated in Table 3. 'Assumes other structures.

Volume 71 Number 5 May 1994 383

a hexagonal close-packed array of oxide anions in which
M3+cations occupy two-thirds of the octahedral holes.
C-M203canbe derived from flourite by removing one-quar-
ter of the anions that generate two types of distorted octa-
hedra. Laz03presents the unusual seven coordination for
the metal atom, with the nearest oxygen neighbors around
La3+ions forming a monocapped octahedron.
&04
Spinels
Few elements form oxides with this stoichiometry that
dictates that the same element be present in two different
oxidation states (Table 5). Mn, Fe, and Co form M304OX-
ides, presenting spinel structure (see below).
Stoichiometries That Yield Other Forms
Layers and Chains
Mzo5
This stoichiometry is shown by elements of the vana-
dium group (Table 5). The pentoxide of this element has a
layered structure, with a characteristic 5- coordination
with one short V-O bond. The pentoxides of Nb and Ta
have many crystalline phases, the most remarkable being
the chains formed by tantalum pentoxide.
M03
This stoichiometry appears in the Cr, Mo, W, and Re ox-
ides (Table 5). Among them, the simplest one is the cubic
Table 5. Transition Metals That Form Pentoxides MzOs,
Trioxides M03, and Spinels M304
structure of ReO-. directlv related to the oerovskite struc-
ture. ~ r ~ ~ f o r m s k i nfhains
i t e in which ihe metal cations
have tetrahedral coordination with two long and two short
Cr-O bonds, whereas Moo3shows a unique layered struc-
ture in which each octahedral MOsgroup shares two adja-
cent edges with similar groups.
.. .
One of the most remarkable cases of ~olvmornhismis
presented by WO.,, which has up to eight phase transitions
uo to 900 X!. All the ohases are distorted structures ofthe
gghly symmetric cuke Re03.
Molecular Solids
Mzo7
Oxides of Mn, Tc, and Re show this stoichiometry (Table
6). Mnz07is a deeply colored oil a t room temperature,
whereas Tcz07and Re2O7are yellow volatile solids. Mnz07
and Tcz07 are molecular even in the crystalline state.
Rez07vaporizes as molecules of the same type, but the
crystal has a layer structure in which equal numbers of
metal atoms are in tetrahedral and octahedral coordina-
tion.
There are only two metal tetroxides, Ru04 and 0 ~ 0 ~ .Figure 3. Clystal structuresof spinel structure AB204 (shadedcircles,
Both exist as regular molecules in the crystalline and metal cations; hollow circles, oxide anions).
384 Journal of Chemical Education
Table 6. Transition Metals That Form Tetroxides M04
and Heptoxides Mz07
vapor states. At room temperature they are solids with low
meltingr25 and 40 .CI and boilingpoints (100 and 101 'CI.
Complex Structures
Some mixed oxides adopt uncommon, complex struc-
tures, such as perovskite and spinel, that show interesting
physical and electronic properties. Perovskovite plays a
role in high temperature supercouducting, and spinel is of
interst due to the magnetic properties of the oxides that
show it.
Spinel
Spinels form a large class of compounds whose crystal
structure is related to that of the mineral spinel itself,
MgA1204. The general formula is AB2X4,and the unit ceU
contains 32 oxygen atoms in almost perfect cubic close-
packed array (i.e., A&6032) (18). The structure can be de-
scribed as being built up of alternating cubelets A04 and
B404(Fig.3). The four oxygen atoms have the same orien-
tation in the eight cubelets, thus forming the cubic close-
packed network. They coordinate cation A tetrahedrally
and cation B octahedrally.
Depending on the degree of occupancy of the holes in the
. can be normal or inverse. In the
oxveen network.. soinel
n&al spinel structure eight metal atoms (A)occupy onc-
eighth of the tetrahedral sites. and 16 metal atoms (R, oc-
cupy one-half of the octahedral sites. In the inverse spinel,
A (divalent cation) is placed in the octahedral holes,
whereas B is placed in octahedral and tetrahedral holes.
Lattice energy calculations based on a simple ionic
model indicate that the normal spinel structure should be
the more stable. Co and Fe sninel do not conform to this
expectation, probably due to t&eeffect of ligand field stabi-
lization energies on the site preferences of the ions.
Pernuskite
To introduce the pemvskite structure we first examine
the related but simpler Re03structure, which consists of
corner-shared octahedra (Fig. 4). Alternatively, the unit
cell can be described as formed by Re atoms at the corners
of a cube and oxide anions on the edges. The presence of
corner-shared octahedra can be clarified by extending the
structure to more than one unit cell:
.*.--.
- -- - - -.
-
SPINEL

Figure4. Cubic structure d ReO, (0 ~ e ' +ions, 0 oxide anions).Per-
ovskite structure (0 metal cations. 0oxide anions, @ central atom.)
" .
ReO. structure is verv onen.. and in the center it has a
large hole with coordination number 12. Perovskites have
the general formula ARO.,, in which the 12-coordinate hole
in ReO? is occupied by a large A ion. The 0 inn is generally
0'-or F.The structure is oRen observed to be distorted so
that the unit cell is no longer centrosymmetric.
Electronic Structure in Transition Metal Oxides
ChemicalApproaches
The description of the electronic structures of transition
metal oxides presents many more problems than that of
geometric structures.
The Ionic Model
I n a first aproximation, the ionic model can be used to
predict heats of formation and many of the chemical and
ohvsical orooerties of transition metal oxides. Thev are de-
k i e d a s fonii compounds with the formula ~ ~ 0 ~ f o kby
n e d Pure Ionic Compounds
0'-anions and M"+catious.where n is 2-8.
The simple ionic model with the Born-Lande expression
provides goad values of monoxide and dioxide lattice ener-
gies.
The agreement is particularly good when introducing the
correction of the cwstal field solittine (191.a oerturbation
that introduces peXodical varikions-in lattik energies as
well as in M-0 distances.
Molecular and Covalent Crystals
For higher valent oxides, because electronegativity of
the metal cation increases with oxidation number, the
metal-oxveen bond becomes nredominantlv covalent. and
the oxidescan no longer be d e k b e d as ion&. ~ccordihgto
this orediction. oxides with formula M907and
- . MOaare low
melthg moleklar solids.
Although there is good agreement between experimental
and calculated values using the Born-Lande expression,
the covalent model more closely describes the bond in sec-
ond and third transition series oxides. In particular, sev-
eral low valent oxides a t the end of the series (e.g., ZnO,
PdO, CuzO, and Ag20)are better described as giant cova-
lent &ol&;les thanas ionic compounds: covalent interac-
tions dominate over electrostatic interactions, and cwrdi-
nation numbers and geometry are determined by covalent
interactions (12).
Interstitial Compounds
Moreover, monoxides a t the beginning of the first transi-
tion row are in many aspects more like alloys than like
ionic compounds due to the existence of metal-metal bonds
in the three directions of the lattice. Alternatively, these
monoxides have been explained as interstitial compounds
in which oxygen would be placed in holes of the metallic
network, forming a cubic close-packed structure (12).
This group of oxides could then be classified as metallic
because they have metal-metal bonds and high electrical
conductivities. A direct relationship has been established
between these two features assuming the metallic charac-
ter is the conseouence of the metal-metal bonds. Never-
theless, this sim'ple hypothesis does not explain the high
conductivitv of ReO* because metal-metals bonds are not
possible there.
Band Structure
So far I have discussed the chemical and physical prop-
erties of these inorganic solids in terms of covalency and
electrovalency. everth he less, these two approaches are not
satisfactory when trying to explain electronic properties
such as electrical conductivity. For this we need the band
theory in which the ionic or covalent character of the bond
does not have relevance. Instead. solids are classified a s
conductors, semiconductors, or ikulators on the basis of
their band gap E, According to this magnitude,
Ti0 is a conductor (Ep= 0).
CuzOis a semicondudor ( E p=,2.2eV).
MnO, FeO, COO,and NiO are insulators ( E p= 6 eV).
In this approach to the study of the bond, the most im-
portant features are the energies and the widths of the
various bands, the energy gap between bands and the
number of electrons involved. To understand the electronic
behavior of transition metal oxides, we will look a t band
structures of the monoxides of the first transition row.
Usually in a pure ionic oxide (e.g., MgO) each ion has a
closed-shell electron configuration. Thus, the valence
band, which forms the highest energy filled level in the
solid, should be derived from the highest energy occupied
orbitals of the oxide anion. Likewise. the lowest enerw
empty level-the conduction band-shbuld be formed frc&
the lowest energy empty orbitals of the metal cation. As a
consequence all bands are either completely empty or com-
pletely full, so ionic compounds are generally insulators.
Dansition Metal Monoxides
The basic band diagram for transition metal monoxides
(Fig. 5 ) is similar to that of other ionic compounds, showing
a valence band, basically an oxygen 2p band, and a conduc-
tion band of metal character. Because the lowest enerw
unoccupied metal orbitals are the d orbitals, the condue-
tion band is usuallv called the d band. As shown below. the
d band can be split by ligand field effects similar to those
found in transition metal complexes. Because this band
can be partially occupied with d electrons, transition metal
com~oundscan be semiconductor or conductor.
&hough the description above is easy to understand, in
a rigorous description the valence band is a bonding com-
bination of oxygen and metal orbitals, whereas the conduc-
tion band is an antibonding combination. Nevertheless.
the description of both bands, such as the oxygen 2p and
the metal 3d, is useful because i t denotes the atomic
orbitals' principal constituents of each level.
According to this description T i 0 2 should be semiconduc-
tor or insulator because Ti4+has a 3d0 configuration (with
a band gap of 3 em. On the contrary, T i 2 0 3 with a 3d1 con-
Volume 71 Number 5 May 1994 385

u ( ~ ~ ts ,a p lbands)
f tion must be considered for all M2+and 0"ions in the crvs-
Valence band
(02,)
Figure 5. Band diagram of a transition metal oxide indicating Valence
band, conduction band, and band gap G; (a) d band empty: (b) d
partially filled.
figuration has one electron per atom in the d band and can
show metallic conductivity (at high temperatures).
Molecular Orbital and Band Diagrams
Another approach to the study of the electronicstructure
of monoxides of the first transition row begins with depict-
ing the molecular orbital diagram for the basic unit, that
is, the first coordination polyhedra of oxygen anions
around metal cations. Then the band structure is obtained
by orbital overlapping and delocalization. Although this
approach can be considered an oversimplification of the
real electronic structure. it reoresents a serious effort to
correlate two approaches that generally are olrered w the
students as mmpletcly separate: Molecular Orhital theory
and bnnd theory. This unifying view proposed by Duffy (141
is an alternative to thc dlchotomv of-bonds or bands" of-
fered by other authors (15,16).
As dicussed above transition metal monoxides have the
highly symmetric structure of rock salt, the basic polyhe-
dra being MOB,an octahedron of oxide anions around M2+
cations. Using the metal 3d, 49, and 4p atomic orbitals,
with symmetry ta and e, (3d orbitals), al, (4s orbital), and
tl, (4p orhitals) and taking into account only a overlap with
p orbitals from oxide anions, we get the molecular orbital
diagram shown in Figure 6a.
The crucial differencebetween the structure of three-di-
mensional monoxides and isolated MO6 units in hexa-
coordinated complexes (e.g., M(HZO)~~+), is that any partic-
ular 02-ion in a M06 unit is also part of five other MO6
units. Therefore, its interactions with one particular M2+
ion is modified by the influence of the other five M" ions
(a)
Flg~re6 (a) Mo ecular on, tal scheme showlng a lnteractlon for MO,
unrs. (b) ban0 d agram for so o MO wewed in terms of condens ng
M 0 6 mo ecdlar orblta s
386 Journal of Chemical Education
that surround it. The overlanoine is not confined to seven
atoms hut is spread all over i i e &stal. Thus, this interac-
tal.
In this wav an enormous number of molecular orbitals
~ ~~ ~
will be with bonding and antibonding character.
The number ofmolecular orbitals within bondiue and anti-
bonding sets is extremely high. Thus, the energy separa-
tion between them is so small that an enerev continuum is
produced, resultingin the band structure p&ted in Figure
6b.
As shown in the diagram, the valence band comes from
bonding molecular orbitals (e,, t,,, and al,) and the conduc-
tion band from nonbonding d levels (tz,). Additionally,
there is an empty band of higher energy arising from the
antibondmg orbitals e,i, a$, and tyx. The conduction band
would be partially filled in conducting oxides, such as TiO,
with Ti2+ionsshowing configurations a. Monoxides with
ions having an empty &,band could be either semiconduc-
tors or insulators, whereas compounds in which with this
band is totally filled (e.g., NiO) with configuration t&, are
insulators.
The Hubbard Model
-
This simole model has manv advantaees because it
seems to reconcile microscopic and macroscopic ap-
proaches to the bond structure of these compounds, and it
satisfactorily explains both physical and chemical proper-
ties. Nevertheless. a ~roblemremains. Accordina to this
simple band diagram all monoxides with a filled
band should show metallic conductivity. Although elec-
tronic distributions ib d levels for Mn2+,Fe", and Co2+ions
are t3 2~tzpe,,
4 2
~ and, t&;, all their monoxides are insulator.
Electron Repulsions and Localization
The reason for this failure of the simple model are the
reoulsions between electrons that have been nedected so
far. These repulsions tend to keep electrons localized on
individual atoms. Metallic properties are then obsewed
only when there is a strong tendency to band formation
due to an effective overlap. Thus, the high electrical con-
ductivity of Ti0 and VO and the low values of the other
monoxides from the first transition row can be attributed
to the larger overlap of d orbitals at the beginning of the
first transition series, which is much more effective than a t
the end. This is a consequence of the contraction of d orhit-
als along the series due to the increase of nuclear charge.
The well known Hartree-Fock approach assumes that
electrons move independently in a potential field that in-
cludes the average repulsion from other electrons. This ap-
~roximationworks well in many situations. However, for
solids that show small interatomic overlap the effect of
electron repulsion becomes more important and cannot be
treated as an average potential. The most useful approach
to electron repulsion in this case is the Hubbard model,
which assumes that the only important repulsion effects
occur between two electrons on the same atom. Although
reoulsions between electrons on different atoms are not
nlgligible, the intraatomic effect seems to be the main rea-
son for the breakdown of the band theorv.
For an array of atoms with a single valence electron in
which the overlap between orbitals is small, in the ground
state each electron will be localized on one atom. This is
due to electron repulsion when trying to move the electron
to another atom. The energy required to remove one elec-
tron from one atomic orbital is the ionization potential IP.
Placing this electron in one atom already occupied, we get
the electron affmity of the neutral atom EA. The energy
required to move the electron is given by
This quantity can be interpreted as the repulsion energy
between two electrons on the same atom.
Bandwidth and Overlapping
The effect of the electron repulsion is to make the par-
tially filled band insulating when the interaction between
atoms is small. The bandwidth will increase when the
overlapping is more effective. When there is no overlap-
ping, the bandwidth is zero and atomic levels will result.
The lower level corresponds to the energy of singly occu-
pied orbitals (IP), and the higher (EA) to the energy ob-
tained aRer putting a second electron in the orbital.
The gap, equal to U, is the energy required to excite an
electron, displacing it to another atom. This gap, often
called Mott-Hubbard splitting, is a wnsequence of elec-
tron repulsions. Each level can be broadened by interato-
mic overlap, and the gap disappears when the bandwidth
Wand the repulsion parameter U are equal. Thus, the
band theory becomes useful when W > U.
Global Diagram of Energy Levels, Bands, and Splittings
Aglobal approach to the study of the bond in these mon-
oxides that takes into account all the significant wntribu-
tions has been included in Figure 7. The f r s t step for cal-
culation of the energy diagram of transition monoxides is
to consider the process of forming free ions M2+and 02-.
The two levels obtained correspond to the difference in en-
ergy between the electron afinity LEA] of oxide anions and
ionization potentials of the divalent metal ion (ZIP, (Fig.
7a1:
E,=EA-DP (3)
Madelung Potential, VM
The main correction to this initial estimate is to consider
the strong electrostatic potential experienced by the ions
in the solid due to the surroundina ions of opposite charpe.
We must take into account not oniy the nea;kst.neighb&r
ions but also the potential from distant shells of ions in the
crystal lattice. This potential involves the Madelung con-
stant of the lattice AM,as in the calculation of lattice en-
ergy in the simple ionic model. This potential is thus called
Madelung potential and is related to the interionic dis-
tance r. by
F E E IONS MAELUNG POLARIZATION OVERLAPPING
POTENTIAL
m,,
FlgLre 7 Schemallc oerlvatlon of energy evels for monoxloe MO of
an element of the f m trans t on serles. (a)freefons evels. (0) ~onsin
tne Madel~ngpotent al. (c) poar zaton ncl-deo showlng the HLO-
bard gap J forlne 3a orblta s, (dl over ap gw ng narrow 30 oand w lh
band gap Eg;(e)wide band giving a metallic compound.
The estimate of the band gap that includes this potential
is (see Fig. 7b)
Polarization Effects
When dealing with solids we must consider polarization ef-
fects, appearingwhenever one electronis moved from one site
to another. An approximate estimate of this effect can be
made by wnsidering the solid as a continuum with relative
dielectric wnstant %. If a charge q spread over a sphere of
radius r is moved from the vacuum into the solid, the electro-
static polarization gives an energy change equal to
Mott-Hubbard Splitting
The polarization of other electrons towards the vacant
hole and away from the extra electron lowers the energy
required to excite the electron. Consequently, the values of
the Mott-Hubbard potential measured in solids are much
lower than the values obtained from the difference in en-
ergy between the atomic levels. Because the 3d orbitals in
a transition metal are partially filled, we must consider
the energies due to loosing or gaining one electron.
The Mott-Hubbard splitting is the difference between
these two energies. In the gas phase it would be the differ-
ence between the third (eq 8) and the second (eq 7) ioniza-
tion energies: about 15 eV. Polarization effects in the solid
reduce this magnitude as shown in Figure 7c, the final
value being about 3-5 eV.
Overlapping of Orbitals
Overlapping of orbitals causes the bandwidth shown in
Figure I d and 7e. In the first case overlapping is insuffi-
cient to overcome the MoteHubbard splitting. Thus, a
band gap (E,) appears, making the oxide an insulator (e.g.,
MnO, NiO, and COO).In this case both the highest energy
occupied levels and the lowest energy empty levels have 3d
character. Thus, they differ from the other nontramition
metal oxides whose highest energy occupied levels have
basically 0 2p character, whereas the lowest energy unoc-
cupied levels have metal ns character.
Figure 7e shows what happens when, due to a more ef-
fective overlap, the d band becomes broader, thus forming
a partially filled band and giving a metallic compound.
This energy-level diagram is applicable to metallic oxides
Ti0 and VO.
Conclusion
The schematic diagram in Figure 7 ends the brief survey
of theories currently applied to explain the electronic
structure of transition metal oxides. It is our hope that
after having shown facts and theories concerning this
group of oxides, the idea that transition metal chemistry
goes beyond coordination compounds has gained adher-
ents.
Note added in Proof: After submission of this article, a
book on this topic has been published (20).
Volume 71 Number 5 May 1994 387
Acknowledgment 9. B ~ I ~ IKWJ: LY, K T J them E ~ U C1.~ ~ 1 . 6 8 . 8 7 5 - 8 7 ~ .
10. Wells,A.FStmduml ImganIcChhmiitry; OxfordUniversity: Oxford. 19% Chap
The author thanks Spanish DGICYT (project number PB ter 12.
92.067) for financial and Aria Garcia from the ll. G u t i m z Rios, E. Quimimlnorganim; R e v e r b Barcelona, 1978: Chapter 28.
12. Phillips. C. S.G:Williams,R. J. P Inorganic C h i s f r y ; OxfordUniuersity: London,
ICMSE for drawing the figures. 1965;Chapters 24-26.
13. Cox. P A. The E k f m n i e Structure a d C h i s t r y offhe Sdids; Oxford University:
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388 Journal of Chemical Education