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Antiferromagnetic Induction in High Temperature

Superconductors

While superconductors are fascinating materials to study , they are very practical ,
too ; think of the Magnetic Resonance Imaging (MRI) machines in hospitals , so
invaluable in medical diagnostics . MRIs have large coils of a superconducting
intermetallic compound made of niobium and titanium (Nb0.6Ti0.4 ; Tc = 9.8 K) , or of
niobium and tin (Nb3Sn ; Tc = 18 K) , immersed in a bath of ultracold (4.2 K) liquid
helium . These superconducting coils generate the intense magnetic fields required to
completely permeate the human body .

Scientists study superconductors in many ways . Most of the research with


superconductors is carried out by condensed matter physicists , who examine their
many varied properties . Crystallographers determine their crystal structures .
Materials scientists and technologists develop practical applications for
superconductors ; for example , how the brittle , poorly malleable and ductile
intermetallics NbTi and Nb3Sn can be formed into wires used for superconduction .

The preparation of superconductors is done by solid state chemists , who also try to
devise new chemical compounds that might have that property . That's where the
problem arises . There are no chemical theories or models of superconductivity , as it's
considered to be a physical and not a chemical phenomenon . The long-reigning BCS
theory (from Bardeen , Cooper , and Schrieffer) , is a lengthy mathematical treatise
that makes no mention of chemistry or of any chemical substances (the references are
listed at the end of this web page . Underlined blue hyperlinks can be clicked when
online to download the PDF or HTML file , which will open in a new window) .
However , all superconductors – and “ordinary” electrical conductors , of course – are
elements and chemical compounds which can be described in chemistry terms . How
can we associate the physical phenomenon of superconductivity with the chemical
description of the materials in which it occurs ?

The earliest attempt to correlate superconductivity with the chemical attributes of


superconductors was made by B. T. Matthias , who in the mid to late 1950s proposed
several guidelines (now generally referred to as Matthias's Rules) for optimizing the
superconducting transition temperature , Tc , in alloys of elements and in binary
intermetallic compounds . At that time the superconductors with the highest Tc
values , and consequently of greatest research interest , were intermetallic compounds
with the general formula M3X and having the A15 , or beta-tungsten crystal structure :

The A15 (beta-tungsten) crystal structure for an M3X intermetallic compound . Red
spheres : M atoms ; blue spheres : X atoms . Examples : Nb3Sn (see above) , Nb3Ge ,
V3Si . This molecular model is based on the sketch of the A15 structure in Simon and
Smith's book .

Matthias observed that the higher Tc A15 superconductors always had a Transition
metal element as the M atom (d shell valence electrons were involved) , and the
optimum average number of valence electrons per atom per formula unit was a
maximum of five or seven . In later years and decades researchers refined and
broadened Matthias's Rules , but never succeeded in extending them to ternary and
quaternary compounds (the high Tc cuprate superconductors , for example) . The
highest Tc ~ 22 K for an M3X A15 intermetallic compound (and for superconductors
generally) was achieved for Nb3Ge films in 1973 , and that record stood until 1986–87
with the discovery of the cuprate family of superconductors .

A second approach to explaining superconductivity in chemical , rather than in


physical terms was made in the mid 1970s by the German solid state chemist Heinz
Krebs (University of Stuttgart) . He attempted to correlate the appearance of
superconductivity in solids with the types of atomic orbitals in which the conduction
electrons were located . Krebs summed up his findings as follows :

“The rule that superconductivity is only possible if there exists at least one space
direction not intersected by plane or conical nodal surfaces can only be verified for a
limited number of superconductors . On the other hand , in no case does anything
point against the validity of this rule . In those cases in which the condition of the rule
is fulfilled , superconductivity is found with very few exceptions . We can thus
assume that the principle condition for the occurrence of superconductivity is in fact
the absence of these nodal surfaces”.

Krebs seems to have been one of the few scientists to study the electronic structures of
nonmolecular solids and superconductors from an orbital point of view .
Unfortunately , his concepts apparently were ignored at the time and forgotten (except
by me) . Recently , his rule about nodes in metallic bond orbitals has been overturned
by the remarkable discovery of an ephemeral superconductivity in heavily-doped
(with boron) semiconductors such as diamond , silicon (PDF , 507 KB) , and silicon
carbide (PDF , 1480 KB) . However , his nodal principle still remains valid for
metallic solids and electrical conduction in general ; I refer to it as Krebs's Theorem ,
and have restated it for the metallic bond this way :

“True metals have a metallic bond consisting of a nodeless crystal orbital along at
least one crystal axis , while in pseudometals the metallic bond consists of a crystal
orbital that is periodically intersected by nodes”.

As is well known , Cooper pairs in superconductors have the surprising ability to


tunnel through thin layers of electrical insulators (the Josephson effect and the
Josephson junction) . They are thus able to tunnel through the periodic nodes in the
XOs of semiconductors (XO = crystal orbital = metallic bond = conduction band) in
an energy-free manner , unlike the singlet conduction electrons in semiconductors in
the normal state . Superconductors can thereby circumvent Krebs's Theorem , which
nevertheless remains valid for “normal” electrical conductors . I've discussed these
orbital concepts of the metallic bond , and various types of metallic solids , in another
Chemexplore web page , “A New Classification of Metallic Solids”, to which the
interested reader is referred .

I think it's safe to say that up to now , all of the known “synthetic” (chemical
compounds , not elements , which are “natural”) superconductors have been
discovered in a serendipitous manner . Serendipity is a lucky or unexpected
discovery , and it often plays an important role in scientific research . Someone will
produce a material that has an extraordinary property that makes it of great interest .
That material is then widely studied , and usually many of its analogues are prepared
and examined . I believe this is true for every new type of superconductor discovered
so far . None were designed and synthesized from first principles , simply because
there are no first principles , in the chemical sense , for superconductors . In scientific
philosopic terms , Matthias's Rules and Krebs's Theorem are inductive (deriving a
general law from specific examples) ; they followed from a study and classification of
existing materials , which were obtained from serendipitous discoveries . What is
needed is a deductive model (a predictive law , from which specific examples are
derived) , one that is based on a broader approach to understanding the phenomenon .
Combining basic physical and chemical concepts , an entirely new model is
constructed , from which novel superconductor candidate compounds can be designed
, synthesized , and tested . The results from these predictions can then be used to
refine and extend the model , or to refute it . If the model is successful , scientists will
no longer have to rely on serendipity to obtain a fresh supply of new superconducting
materials for their research . The objective of this web page is to bring forward such a
deductive model of high temperature superconductors and from it make several
predictions for the design and synthesis of new high Tc compounds .

The Antiferromagnetic Model of High Temperature


Superconductors

I began studying superconductors in 1990 after reading about the new high Tc cuprates
in the popular press , but quickly became frustrated with the total lack of any sort of
chemical explanation for them . What chemistry there was of the cuprate materials
merely involved chemical “cooking”, without any significant theoretical input from
chemists . As mentioned above , the dominant BCS theory was purely mathematical
and completely divorced from the actual chemical materials (elements and
compounds) comprising the various superconductors .

The high Tc cuprates provided two important clues about their physical and chemical
natures , and how they could be linked together . The first clue was the
antiferromagnetism in the copper oxide precursors . The key ingredient in
synthesizing all of the cuprates is copper(II) oxide , CuO , a jet black , refractory (m.p.
1326 ºC) solid which is known to be antiferromagnetic (TN = 230 K , – 43 ºC) . This
antiferromagnetism was often retained when CuO was chemically combined with one
or more other compounds to form more complex cuprates , such as La2CuO4 .
The copper(II) in La2CuO4 is 3d9 electronically , so it will have at least one unpaired
singlet valence electron . According to the simple equation for calculating the spin-
only magnetic moment µ for n unpaired electrons , µ = [n (n+2)] ½ , the ninth singlet
electron in La2CuO4 should produce in it a magnetic moment of 1.73 BM (Bohr
magnetons) . However , Arjomand and Machin measured a much lower magnetic
moment for the compound : 0.69 BM at room temperature (300 K) , and 0.34 BM at
liquid nitrogen temperature (80 K) . These results suggested that La2CuO4 is indeed
strongly antiferromagnetic , even at room temperature . Many subsequent studies of it
confirmed these early findings and provided much more information about La2CuO4 .

Lanthanum copper(II) oxide is non-metallic , but it can be converted by the chemical


process of oxidative doping into a metallic solid . When La2CuO4 is doped with Ba2+
cations (i.e. replacing some of the La3+ with Ba2+) , an equivalent amount of Cu2+ must
be oxidized to Cu3+ in order to maintain electrical neutrality in the system . Thus , the
doping process created a copper(II)–copper(III) mixed-valent compound which
proved to be metallic . The German-Swiss researchers Bednorz and Müller discovered
in 1986 that this barium-doped La2CuO4 was superconducting at a new record high
temperature of around 30 K . Several months later , by substituting smaller Sr2+
cations for the larger Ba2+ , they prepared the analogous cuprate (La0.925 Sr0.075)2 CuO4 ,
whose Tc was somewhat higher , at 38 K .

In the Spring of 1987 the combined Chu and Wu research teams announced their
synthesis and study of YBCO , the first liquid nitrogen range cuprate superconductor
(Tc ~ 93 K) . Their discovery began a frantic search for more high temperature
superconducting cuprates with even higher transition temperatures . YBCO is also a
copper(II)–copper(III) mixed-valent compound with the ideal empirical formula
YBa2Cu3O7 . Its Cu(II)–Cu(III) can be quickly seen by displaying YBCO's “valence
counting formula” : (Y3+ Ba2+ Ba2+)(Cu2+ Cu3+ Cu2+)(O2-)7 . It's interesting to note in
this regard that Arjomand and Machin prepared the two pure , homovalent precursors
to YBCO , BaCuO2 and YCuO3 , back in 1975 . They found the former compound to
be – astonishingly ! – ferromagnetic , and the latter material had high spin octahedral
Cu3+, that while paramagnetic , became mildly antiferromagnetic when cooled to 80 K
. However , YBCO has a completely different crystal structure than either BaCuO2
and YCuO3 , with radically different magnetic and electrical properties than them .

All of the high Tc superconductors were found to have mixed-valent metal cations
(mostly Cu2+ and Cu3+) , and that provided the second important clue – the
“chemistry” one – about high temperature superconductivity . Before reviewing the
role of mixed-valent chemistry , though , I'll first outline the significance of the
“physics” clue , that of antiferromagnetism .
The Transition metals and their compounds display a wide range of magnetic
properties such as Curie paramagnetism , Pauli paramagnetism , ferromagnetism ,
ferrimagnetism , and antiferromagnetism , to name five of the commoner magnetic
ordering states in the solids . Such conditions are produced by the valence shell d
orbital electrons in the metal atoms and their cations . The second type of magnetism ,
Pauli paramagnetism , is produced by the spins of the mobile , free electrons above
the Fermi level EF in the metallic bond . Strong ferromagnetism in metals such as
iron , cobalt , and nickel is associated with the magnets of everyday experience ,
although a weaker ferromagnetism can also be found in certain Transition metal
compounds such as chromium dioxide .

All electrical conductors and superconductors are metallic solids , having a metallic
bond (or conduction band , for the physicists) throughout their lattice . In any one
given sample of a metallic solid there is a single metallic bond , comprised of
continuously overlapping atomic orbitals , which form one single lattice-wide crystal
orbital , XO , containing the valence shell electrons associated with the metallic bond .
The Fermi-Dirac distribution assigns these electrons to a vast number of energy levels
corresponding to the number of participating metal atoms , pairing them two by two
according to the Pauli exclusion principle . In most common metals , about 99% of the
electrons in the metallic bond are thus spin-paired at room temperature , while about
1% of them remain as unpaired singlets in higher energy levels . The boundary
between the paired and unpaired electrons in the XO is the Fermi level , EF . The
unpaired electrons above EF are the free , mobile electrons that are responsible for all
the properties so typical of the metallic solids : electrical conduction and
superconduction , high thermal conduction , metallic luster (high reflectivity) ,
metallic colours , opacity , and Pauli paramagnetism , as noted above .

While it's the mobile singlet electrons above EF that are the electrical charge and
energy carriers in ordinary conductors , it's pairs of electrons – the famous Cooper
pairs – that are the electrical carriers in superconductors . The electrons in the Cooper
pairs are spin-paired , that is , their magnetic spins have an antiparallel orientation , in
a manner similar to the spin-paired electrons in the atomic kernels and in the covalent
bond , for example . At first glance , it would seem that the static electric field around
the electrons would cause them to be repelled from one another . However , a simple
calculation involving High School physics (Coulomb's Laws of Electric Force and
Magnetic Force) shows that the magnetic field around the electrons , derived from
their spins , is much stronger than the corresponding electric field :
Coulomb's Law of Electric Force is simple and straightforward , and is in all of the
physics textbooks I reviewed on the subject . However , Coulomb's Law of Magnetic
Force is by comparison little known . It turns out that the force relationship between
two (macroscopic) magnets is rather complex , and the equation for the magnetic
force used above is a simplification , as explained in the competent Wikipedia article ,
“Magnetic Field” :

“The force between two magnets is quite complicated and depends on the orientation
of both magnets and the distance of the magnets relative to each other . The force is
particularly sensitive to rotations of the magnets due to magnetic torque .

In many cases , the force and the torque on a magnet can be modeled quite well by
assuming a “magnetic charge” at the poles of each magnet and using a magnetic
equivalent to Coulomb's law . In this model , each magnetic pole is a source of an H-
field that is stronger near the pole . An external H-field exerts a force in the direction
of H on a north pole and opposite to H on a south pole . In a nonuniform magnetic
field , each pole sees a different field and is subject to a different force . The
difference in the two forces moves the magnet in the direction of increasing magnetic
field and may also cause a net torque .

Unfortunately, the idea of “poles” does not accurately reflect what happens inside a
magnet (see ferromagnetism) . For instance , a small magnet placed inside of a larger
magnet feels a force in the opposite direction . The more physically correct
description of magnetism involves atomic sized loops of current distributed
throughout the magnet” .

A magnetic force equation , more complicated than that of Coulomb's Law , is


provided in another Wikipedia article , “Magnetic Moment”. The discussion of
magnetic force in these two Wikipedia articles is more relevant to the macroscopic
(eg. bar and horseshoe) magnets of of our common experience . Keep in mind that the
electrons in a Cooper pair are the simplest , smallest , and most fundamental magnets
that can exist ; in fact , their magnetic pole strength (magnetic flux) is considered to
be the quantum unit and is called the “fluxoid” (2.0678 x 10-15 weber) . Also , in
Cooper pairs the two electrons are locked into a perfectly antiparallel orientation to
each other , so there is no magnetic torque between them . In such a simple ,
elementary situation I believe Coulomb's Law of Magnetic Force can be correctly
applied to derive a reasonably accurate comparison – the Fm / Fe ratio – of the
magnetic and electric forces between the two electrons .

The critical requirement is that the two electrons are in an antiparallel orientation to
each other in order for the magnetic field force to surpass that of the electric field .
That being the case , the two electrons can associate with each other in the Cooper
pair . In fact , the Fm / Fe ratio may be double that indicated in the calculation above ,
which applies to a single set of magnetic poles :
I'm speculating here , but possibly the Fm / Fe ~ 2400 case might apply to Cooper pairs
below Tc , while at Tc the magnetic spins reorient to the weaker Fm / Fe ~ 1200 case .
Then , as the Cooper pairs scatter off lattice atoms , their magnetic spins interact with
those of neighbouring lattice atom electrons , and the pairs are torn apart :
Another possibility might be the thermal promotion by energy packets (kT) of the
antiparallel electrons into singlet electrons with a parallel orientation , which forces
them apart and breaks up the Cooper pairs :

The Fm / Fe ratio , which is overwhelmingly favourable for the attractive magnetic


fields about antiparallel electrons , might also explain pairing of electrons in other
environments , such as in the atomic orbitals of the kernels (hence a rationale for the
Pauli exclusion principle) and as a minor contributor to the strength of the covalent
bond . Since the strength of both the magnetic and electric forces is inversely
proportional to the square of the separation distance between them , the closer
together the two associating antiparallel electrons are , the much stronger the
attractive magnetic force between them will be . The range of transition temperatures
of superconductors , from near Absolute Zero to the present-day record of 138 K (at
ambient pressure) , is closely related to this separation distance (coherence length)
between the two electrons in the Cooper pairs .

The pairing of electrons participating in the metallic bond occurs both in physical
space (across the lattice dimensions) and in energy space ; that is , each pair of
electrons is at the same energy level . However , they may be very widely separated
physically , at opposite ends of the crystal , or they may be near to each other , maybe
even on neighbouring atoms . This applies to both the electron pairs below EF , and to
the Cooper pairs that form above EF . Because the Fermi-Dirac distribution limits the
population of mobile , free electrons above EF to roughly 1% of the entire population
of metallic bond electrons , they are widely distributed , statistically , across the
crystal lattice . Thus , their coherence lengths tend to be very long . The absolute
value of the magnetic force between any two sets of antiparallel electrons above EF ,
which might otherwise be able to couple them , must be virtually nil . The pairing
mechanism in such superconductors will therefore be that of phonon mediation , as
described in the BCS theory . Once the phonons have pushed the electron pairs
together , the magnetic coupling force can then link them together into Cooper pairs .

In effect , the Fermi-Dirac distribution in conventional metallic solids inhibits the


formation of Cooper pairs . The Fermi-Dirac distribution is a fundamental attribute of
metallic bonds and is unavoidable , but we can circumvent it by inserting anions
between the metal atoms (now cations) . The anions' valence shell electrons will
participate in the metallic bond and increase its population . Even better , the anions'
electron pairs will form the paired electron population below EF , leaving the cations'
singlet valence electrons above EF . We can now have neighbouring singlet electrons
above EF , which will bring them very close together , i.e. with short coherence
lengths :

“These new pairs [in the high Tc cuprates] differ from BCS pairs [in the low Tc
classical superconductors] in one respect at least : the distance between the charge
carriers of each pair in the new superconductors is much shorter , by a factor of
around 100” (G. Vidali , p. 137) .

A striking example of how non-metal atoms can provide their electron pairs to the
metallic bond is that of rhenium trioxide , ReO3 , whose electrical conductivity is a
remarkable 149,300 ohm-1cm1 (ambient) , comparable to that of many common
metallurgical metals . Its parent element rhenium , with a hexagonal close-packed
(hcp) crystal structure , has a much lower electrical conductivity , 58,140 ohm-1cm1
(ambient) . Rhenium trioxide has a very simple cubic crystal structure :

Rhenium trioxide . Blue spheres , octahedral rhenium(VI) ; green spheres , linear


oxygen . ReO3 has a strong framework of Re–O covalent bonds , covered with a Re–O
metallic bond .
It's quite obvious that the oxygen linking atoms are participating with the rhenium
atoms in the metallic bond in ReO3 . Rhenium trioxide is discussed at some length in
the Iron web page . I've proposed it as an excellent example of a compound having a
bilayer metallic bond , in which the nonmetal (oxygen) atoms provide the paired
electrons for the lower layer (below EF) , and the metal atoms' (rhenium) singlet
valence electrons occupy the upper layer (above EF) . Despite its high ambient
electrical conductivity , ReO3 never becomes superconducting (PDF , 258 KB) , even
very close to Absolute Zero . This is because it isn't antiferromagnetic ; rather , it has
the Pauli paramagnetism so typical of the common metallurgical metals .

Metallic solids with direct metal–metal bonds , such as all the metallurgical metals of
common experience , their alloys and intermetallic compounds , and synthetic metals ,
will thus be adversely affected by the Fermi-Dirac distribution in the sense of being
unable to superconduct at higher temperatures (or at all) . Twenty-nine metal elements
are known to superconduct at ambient pressure (several more , and a few non-metal
elements as well , can superconduct when highly compressed) , but only at a few
kelvins above Absolute Zero . On the other hand , all of the genuine high temperature
superconductors (the cuprates) have a bilayer Cu–O metallic bond . I've discussed
several examples of compounds with a bilayer metallic bond , including that of YBCO
, in another web page , “A New Classification of Metallic Solids”, to which the
interested reader is referred .

The third prominent feature of all high Tc superconductors is that they have mixed-
valent cations as the electronically-active components of the materials , i.e. they
participate in the metallic bond . There are four recognized types of mixed-valent
compounds , which are now universally referred to as the Robin-Day classes , named
for the most prominent researchers in that field , M. Robin and P. Day , whose wide-
ranging survey of mixed-valent compounds , published in 1967 , is still the definitive
review of the topic .

Only Class II is able to provide high temperature superconductor candidates . Classes


I and IIIA are insulating or poorly semiconducting materials ; the Class IIIB synthetic
metals , while highly conductive , either become insulating when they are cooled
down , or they may superconduct , but only near Absolute Zero . They have direct
metal–metal bonds with no participating anions , so all of their metallic bond valence
electrons are subject to the Fermi-Dirac distribution , which greatly reduces the
population of their free , mobile electrons above EF , as mentioned above . In Class II ,
the anions or non-metal atoms separating the electronically-active cations are able to
participate in the metallic bond , donating their valence shell electron pairs to the
lower layer of the bilayer metallic bond in which they participate . In my web page ,
“A New Classification of Metallic Solids”, I expanded Robin-Day Classes II and IIIB
into eight new types of metallic solids . Superconductors can be found in all four of
the true metal classes , but only Class 3 can provide high temperature superconductors
. Participation of the anions or non-metal linking atoms in the metallic bond , i.e. a
bilayer metallic bond , is an essential condition for high transition temperature
superconductivity .

In Robin-Day Class II mixed-valent compounds the valence electrons have an


extremely fast resonance over the anions and between the cations . For example , in
magnetite [Fe3O4 , (Fe3+tet – Fe2+oct – Fe3+oct) O4] the 3d6 valence electron on the
octahedral Fe2+ cations can resonate with the octahedral Fe3+ cations (but not with the
orbitally mismatched tetrahedral Fe3+ cations) :

“......the magnetic fields at the octahedral sites are indistinguishable , indicating an


oscillation of valence [electrons] more rapid than 108/sec . On the other hand , at 85
K , the Fe(II) and Fe(III) ions in the octahedral holes can be distinguished as expected
for a Class II system” (Robin and Day , wide-ranging survey , p. 304) .

There is no thermodynamic barrier to such an electron resonance . Consider the redox


situation in a sample of a homovalent copper(II) oxide compound . Suppose an
electron is transferred by resonance from copper(II) cation A to copper(II) cation B .
Cu2+A becomes Cu3+A , while Cu2+B becomes Cu1+B . The redox equations for this
electron transfer are as follows :

Cu2+A – e- -------------> Cu3+A ........... E0ox = – 2.4 V

Cu2+B + e- -------------> Cu1+B ........... E0red = 0.153 V

Net reaction : Cu2+A + Cu2+B -------------> Cu3+A + Cu1+B ........... E0T = – 2.247 V

The very large negative cell potential for this reaction – the disproportionation of
copper(II) to copper(I) and copper(III) – indicates that it is highly unfavourable
thermodynamically at STP and is essentially impossible . The copper(II) 3d9 valence
electrons are strongly pinned on their respective kernels , and thus homovalent
copper(II) oxide compounds are insulators (or poor semiconductors) .

Now consider what happens in a typical Robin-Day Class II mixed-valent copper


compound , for example in YBCO , with its Cu2+ – Cu3+ – Cu2+ . The copper(II) 3d9
valence electron will resonate with the 3d8 copper(III) . When that happens , the Cu2+A
will become Cu3+A as before . However , now the Cu3+B becomes Cu2+B , as represented
in the following redox equations :

Cu2+A – e- -------------> Cu3+A ........... E0ox = – 2.4 V


Cu3+B + e- -------------> Cu2+B ........... E0red = + 2.4 V

Net reaction : Cu2+A + Cu3+B -------------> Cu3+A + Cu2+B ........... E0T = 0 V

We see from this simple redox analysis that there is no thermodynamic barrier to the
electron resonance in Robin-Day Class II (Class 3) mixed-valent compounds . That's
why they have such extraordinary optical , electrical , and magnetic properties ,
compared to their corresponding homovalent parent compounds , in which the valence
electrons are pinned on their atomic kernels . This extremely fast electron resonance
permits the free electrons in the metallic bond to closely approach other nearby free
electrons ; and , if the two electrons have an antiparallel orientation with respect to
each other , they can magnetically couple together , as discussed above .

A Robin-Day Class II (Class 3) mixed-valency is the “chemical trick” required to


unpin the frozen valence electrons in the metal oxide precursors , thus installing in
them the bilayer metallic bond essential for high temperature superconductivity .
Elementary metals , their alloys and intermetallic compounds , and synthetic metals ,
already have unpinned mobile electrons in their metallic bonds , but because they lack
any participating anions or non-metal atoms , their free electron populations have
been drastically reduced by the Fermi-Dirac distribution , preventing them from ever
becoming high temperature superconductors (if at all) .

A mechanism is now required to arrange the electrons above EF into an antiparallel


spin order . One way to do this is to create a metallic bond within an
antiferromagnetic compound . Then , the antiferromagnetic ordering will also be
imposed on the free electrons , just as it is on the pinned valence electrons in the
parent homovalent compound . This is exactly what Bednorz and Müller did in their
pioneering research with the doping of the strongly antiferromagnetic La2CuO4 . Its
antiferromagnetic ordering translated into an antiparallel spin ordering of the free
electrons in the newly created metallic bond in the doped La2CuO4 , which now
contained both copper(II) and copper(III) , and was a Robin-Day Class II mixed-
valent compound . The antiparallel resonating free electrons were able to approach
each other fairly closely , and magnetically “clicked together” like a pair of
refrigerator magnets (although the resulting Cooper pairs were stable only at relatively
low temperatures , ~ 30–40 K , in that crystal environment) .

The same situation occurred again with YBCO not long after . The compound
YBa2Cu3O6.5 with homovalent copper(II) was partially oxidized in an atmosphere of
pure oxygen to YBa2Cu3O7 , which is a Robin-Day Class II mixed-valent compound .
YBCO is a true metal , with an inverse temperature–electrical conductivity
relationship (its ambient electrical conductivity is around 500 ohm-1cm-1 ) . It has a
bilayer metallic bond , with the linear oxygen linking atoms providing their 2pz
electron pairs to the pi XO . The copper(II) oxide matrix in which the metallic bond is
located in YBCO is strongly antiferromagnetic over a wide temperature range ; thus ,
a strong antiparallel spin orientation was induced in the mobile , free electrons above
EF in the XO . Since virtually all the Cu2+ 3d9 valence electrons were above EF
(because of the bilayer XO) , they were on neighbouring copper atoms and so their
coherence lengths were extraordinarily short . The magnetic coupling force was
therefore quite strong , and the resulting Cooper pairs were remarkably stable . As a
result of all these converging factors , YBCO proved to have a record (at the time , in
early 1987) transition temperature , Tc ~ 93 K , well into the liquid nitrogen (>77 K)
range .

If we examine various superconductors in the other three classes of true metals , we


see that there is little, if any , antiferromagnetic ordering in them . That is , their
kernels are mostly diamagnetic , and they exhibit Pauli paramagnetism , which is
common in “ordinary” metallic bonds . Since there is no antiferromagnetic ordering in
them , their transition temperatures are all very low , usually close to Absolute Zero .
Their superconductivity can be attributed to the BCS phonon-mediated association
mechanism .

The family of ferropnictide (LaOFeAs) superconductors , which I have surveyed in


another web page , is a noteworthy exception . These compounds have direct Fe–Fe
metallic bonds (they can be thought of as iron synthetic metals) , and so are prevented
by the Fermi-Dirac distribution from becoming high Tc superconductors . However ,
their pnictide atom components do seem to have a mild , modest sort of
antiferromagnetic ordering capability on their iron atom neighbours , and the
ferropnictide transition temperatures are in a “medium” range of about 30–50 K , with
a current (February , 2010) record high Tc = 56 K for several related compounds .
Because the ferropnictides have a monolayer metallic bond (i.e. direct metal–metal
bonding) , we can predict that they will never be high Tc superconductors . Possibly
by various chemical adjustments (discussed in the Doping web page) their transition
temperatures might be raised into the low end of the liquid nitrogen range , but they
are unlikely ever to exceed 100 K , in my opinion . Selenium also seems to have the
“magic touch” for inducing antiferromagnetic ordering in certain of the Transition
metal atoms (such as cobalt) to which it is bonded .

Summarizing , the physical basis of all superconductivity is the magnetic coupling of


pairs of free electrons above EF in any environment and at any temperature . For low
temperature superconductivity the BCS phonon-mediated enabling mechanism
“pushes together” the metallic bond free electrons , which are widely separated across
the crystal lattice . For high temperature superconductivity a Robin-Day Class II
mixed-valence resonance unpins the valence electrons , which are in close proximity
on neighbouring cations , and thereby creates a bilayer metallic bond in the solid .
Once the free electrons are brought fairly close together – by whatever mechanism –
they can magnetically couple together into Cooper pairs . However , they must have
an antiparallel spin orientation relative to each other in order for the magnetic force to
apply and be effective .

There are several chemical prerequisites for high temperature superconductivity :

* First , the material must be a true metal [inverse temperature–electrical conductivity


relationship] , with a nodeless XO . Yes , superconductivity can also occur in
pseudometals (because Cooper pairs can tunnel through nodes) as we have seen in
samples of heavily boron-doped diamond , silicon , and silicon carbide , but this
superconductivity occurs only at very low temperatures , close to Absolute Zero .

* Second , the material must have a bilayer metallic bond , so that all the valence
electrons concerned from the electronically active metal atoms will be located above
EF . They will then be located on neighbouring metal atoms and will have very short
coherence lengths , and can strongly couple together magnetically to form reasonably
stable Cooper pairs .

* Third , nonmetallic compounds with homovalent cations must be chemically


converted into Robin-Day Class II (Class 3) mixed-valent compounds with a bilayer
metallic bond ; and ,

* Fourth , there must be antiferromagnetism in the material , either naturally in its


precursor , or induced in it by an external agent . The stronger its antiferromagnetic
ordering , the stronger will be the antiparallel ordering of the free electrons above EF
in the XO and the stronger its Cooper pairs will be . In the following section of this
web page I'll discuss the possibility , with several examples , of modifying non-
antiferromagnetic (i.e. diamagnetic) Robin-Day Class II mixed-valence systems by
intercalating them with nonmetallic antiferromagnetic layers . The metallic bond will
remain in the mixed-valent layers , but hopefully the additive will induce an
antiparallel ordering into its free electrons . Then they'll be able to form Cooper pairs
at a much higher temperature than they would without the antiferromagnetic layers . A
substantially higher Tc of the layered composite compared to the original mixed-valent
compound would be very encouraging for researchers in their study of these new
superconductor candidates .

Any theory is of little value unless it can be tested by various experimental methods ,
by which it is verified , or refined , or refuted . In the following section of this web
page I'll outline the syntheses of several new types of potential high temperature
superconductors , which may provide some evidence to support the antiferromagnetic
induction model described above .

Intercalating Robin-Day Class II Mixed-Valent (and Generally ,


Metallic) Substrates with Antiferromagnetic Induction Layers

The first step in a chemical approach to designing new high temperature


superconductors is to select a suitable antiferromagnetic precursor which can be
modified by some chemical technique or other into a metallic solid . This latter
material should then have a good chance of being a superconductor , and possibly
with a reasonably high Tc . The following Table presents a selection of well-known
antiferromagnetic compounds , together with their Néel temperatures (TN) .
Generally , the higher the TN the better , since below TN the valence electrons are
being organized into their characteristic antiparallel spin régime . Therefore , the
higher the TN the higher the temperature at which there will be an antiparallel ordering
imposed on the mobile , free electrons above EF in the newly-created metallic bond in
the solid . Hopefully any Cooper pairs created at that higher temperature will also be
stable within that particular crystal environment :
A more complete list is provided in the CRC Handbook of Chemistry and Physics , as
noted immediately above in the Table .

It's convenient to think of the mixed-valent cations in Robin-Day Class II compounds


selected for superconductor candidates in terms of triads . The copper triad can be
readily seen in YBCO , YBa2Cu3O7 : (Y3+ Ba2+ Ba2+)(Cu2+ Cu3+Cu2+)(O2-)7 . Materials
in the superconducting state are known to be strongly diamagnetic , which means that
all the electrons in the the electronically-active metal atoms or cations must be
completely spin-paired . In YBCO , the 3d9 valence electrons in the copper(II) cations
form the Cooper pairs , while the Cu3+ base cations ( 3d8) are spin-paired :
Cu3+spCu3+spCu3+sp e22- . Meanwhile , the yttrium and barium cations , and the oxide
anions , are also diamagnetic , so YBCO in the superconducting state is entirely
diamagnetic .

We could also consider a lower-valent , mixed-valent copper triad : Cu0–Cu1+–Cu0 ,


with copper(I) base cations , which are 3d10 electronically : Cu1+spCu1+spCu1+sp e22- .
This triad might furnish some interesting new metallic solids to study , but they would
probably not be high Tc superconductors (if at all) , because copper(I) compounds are
well-known to be diamagnetic , and therefore are incapable of inducing an antiparallel
ordering in their valence electrons . A metallic solid containing such a lower-valent
copper triad would undoubtedly need to be layered with an antiferromagnetic
induction agent in order to become superconducting .

In the Iron web page I proposed the mixed-valent Fe1+–Fe2+–Fe1+ triad , for example in
the novel compounds Fe3OX (X = a chalcogenide anion , i.e. sulfide , disulfide ,
selenide , and telluride) , for incorporation into new superconductor candidates . If the
base of iron(II) cations , 3d6 , can be kept in a low-spin condition (the chalcogenide
anions should ensure that this happens) , the “extra” 3d7 valence electrons on the
iron(I) cations can form the Cooper pairs : Fe2+sp Fe2+sp Fe2+sp e22- . The FeO matrix of
this system is antiferromagnetic [TN = 198 K (–75 ºC)] , so there is a good chance of it
being superconducting at a reasonably high Tc . On the other hand , iron(III) cations ,
3d5 , are permanently paramagnetic because of their odd number of valence electrons ,
so they can never be used as the electronically-active cations in the metallic bond ,
where they would prevent the formation of Cooper pairs . Thus , while the compound
LaFeO3 is antiferromagnetic with an extraordinarily high TN = 750 K (477 ºC) , its
iron(III) cations disqualify it from consideration as an antiferromagnetic precursor
compound .

In actual practice , there are few usable triads that can be derived from the elements
whose antiferromagnetic compounds are listed in the above Table (copper is , of
course , the outstanding exception) . The concept of chemically creating a metallic
bond within an existing antiferromagnetic compound thus turns out to be of rather
limited scope . A more practical approach – and one with a much wider scope – would
be to combine an existing diamagnetic mixed-valent triad with an external
antiferromagnetic induction compound . While most elements have multiple valence
states (especially the Transition metals) and so could theoretically provide us with
many mixed-valence triads – refer to Robin and Day's comprehensive review of
mixed-valence chemistry – I'll discuss only several of the better known ones , because
of the limited available length of this web page .

The first one is the bismuth triad , which is found in the high Tc superconductor
BSCCO-2212 (bismuth strontium calcium copper oxide , Bi2Sr2Ca2Cu3O10+y ; Tc ~ 110
K) :
This molecular model was based on the sketch of BSCCO-2212 by G.-H. Gweon .

It's generally thought that superconduction in BSCCO is in the copper oxide layers :

“The present work on the Bi compounds , as well as similar work on the high-Tc
thallium phases , whose structures also do not contain Cu–O chains , indicates that
superconductivity resides in the CuO2 planes” (Tarascon et al. , p. 8891) .

This might not be correct , as the following simple redox analysis shows . First , here's
a Table of common oxidizing metal species and their standard reduction potentials :
The standard reduction potentials , E0red , for the metal species are all versus the SHE
at STP . However , they were derived either from measurements in aqueous media or
from thermodynamic calculations , so we should be cautious about applying them in a
solid state environment . Nevertheless , they can provide some useful guidance to the
chemist in the design of new superconductor candidates .
Copper(III) , with the highest E0red , is the most powerfully oxidizing metal cation
known . YBCO , with mixed-valent Cu(II)–Cu(III) , is a strong oxidizer , and when
exposed to atmospheric humidity it can oxidize water to oxygen gas and hydroxide
anions . The bismuth triad is Bi(V)–Bi(III)–Bi(V) [Bi(4.33+)] , which is 6s0–6s2–6s0
electronically . The Bi(V) component of the triad is a remarkably powerful oxidizer ,
with E0red ~ 1.8 V ; the mixed-valent triad Bi(4.33+) would have a somewhat lesser
E0red . Consider the unoxidized parent precursor to BSCCO , Bi2Sr2Ca2Cu3O10 . By
valence-counting we see that all of its metal atom components are homovalent :
(Bi3+)2(Sr2+)2(Ca2+)2(Cu2+)3O1020- . Using oxidizing conditions in its preparation (such as
a flowing atmosphere of pure oxygen gas) a small mole fraction , y , of oxide can be
added to the precursor material to obtain BSCCO , Bi2Sr2Ca2Cu3O10+y ; the actual
value of y has never been specified , to the best of my knowledge . This added
increment of oxygen removes some of the valence electrons from the metal atom
components . Will the electron donor be the bismuth(III) or the copper(II) ? Redox
considerations suggest that bismuth(III) is easier to oxidize to Bi(V) than copper(II) is
to oxidize to copper(III) . So the superconductor triad in BSCCO is Bi(V)–Bi(III)–
Bi(V) , not the copper triad .

I should mention an alternate possibility here : that of a pseudo mixed-valent


resonance in BSCCO , in which the strongly oxidizing Bi(V) components try to “take”
the copper(II) 3d9 valence electrons , while the resulting copper(III) kernels
simultaneously try to pull them back from the bismuth atoms . This sets up an ultrafast
resonance between the bismuth(V) and copper(III) centers , with the 3d9 valence
electrons participating in the “tug-of-war” between them . In other words , the 3d9
electrons have been “activated”, just as they are in the genuine Robin-Day Class II
Cu2+–Cu3+–Cu2+ triad :

Bi(V) + 2 Cu(II) <-------------> Bi(III) + 2 Cu(III) ; E0T ~ | 0.6 V |

The electron exchange equilibrium is expected to lie well to the left in the above
equation . The absolute difference between the two E0red values for Bi(V) and Cu(III)
is roughly 0.6 V , written between vertical bars to indicate that it is neither a positive
nor negative value . In this picture , the homovalent copper(II) cations have been
redox-activated by the bismuth(V) components , and so superconductivity would
indeed occur in the CuO2 planes , as claimed by Tarascon and co-workers .

However , I'm interested in exploring the alternate explanation of superconductivity in


BSCCO , provided by the antiferromagnetic induction concept . In this model , the
actual electronic activity is in the bismuth–oxygen layers , with the bismuth triad ,
Bi(V)–Bi(III)–Bi(V) , providing the Cooper pairs for the superconduction . The
copper–oxygen layers are electronically inert , but are strongly antiferromagnetic in
nature , and they impress an antiparallel spin ordering on the adjacent mobile , free
electrons in the Bi–O bilayer metallic bond . Without this external influence , a
diamagnetic Bi–O superconductor would have only a low Tc ; but with a neighbouring
antiferromagnetic induction , much stronger Cooper pairs should be produced ,
resulting in a significantly higher transition temperature (which is about 110 K , in the
case of BSCCO-2212) .

Magnetic induction of any sort in crystalline solids is accomplished orbitally , by an


electron superexchange process . Cox comments ,

“Direct through-space magnetic dipole interaction of spins is far too small to account
for most magnetic-ordering phenomena” (p. 148) .

The electron spin orientations of the cations are mediated by the p orbital electron
pairs of the intervening anions , as shown below for the Cu–O–Bi atoms in BSCCO ,
for example :
Superexchange in this particular case may be facilitated by the pπ –pπ overlap of the
Cu 5pz –O 2pz –Bi 7pz orbitals to form a linear nodeless Cu–O–Bi pi XO . The spin
orientations of the Cu and Bi valence electrons will be synchronized by
superexchange , with bismuths' free electrons copying the antiparallel orientations of
their copper 3d9 partners , which are pinned in the Cu–O lattice .

Generally , the free electrons' spins will mimic those of any sort of magnetic ordering
in the adjacent induction layers . For example , if the induction agent was
ferromagnetic , the spin ordering in the free electrons above EF would be identical ,
i.e. parallel . This is reminiscent of their precise reflection of incident light
wavelengths , which is the physical basis of mirrors .

Such a diamagnetic bismuthate superconductor was discovered by two independent


research groups in 1988 and had a medium range Tc = 29.8 K (onset) . It was a cubic
symmetry perovskite , and was prepared in strongly oxidizing conditions :

0.6 BaO + 0.4 KO2 + ½ Bi2O3 --------- (1) heat at 675 ºC , 3 days ---------

--------- (2) anneal in pure O2 , 475 ºC ---------> Ba0.6K0.4BiO3

Its valence-counting formula is Ba2+0.6K1+0.4Bi3+0.3Bi5+0.7O36- , with a NIOS (non-integral


oxidation state) bismuth valence of Bi(4.4+) , which is quite close to the Bi(V)–
Bi(III)–Bi(V) triad valence of Bi(4.33+) ; the exact triad would be present in
Ba0.67K0.33BiO3 , i.e. 4–5–4 , which is equivalent to 5–3–5 . Ba0.6K0.4BiO3 is a true
metal with a nodeless Bi–O bilayer metallic bond (probably Bi 7px,y,z– O 2py,z) , and
it's a Robin-Day Class II (Class 3) mixed-valence compound . All the ingredients are
in place for the appearance of superconductivity in it , but one key component is
missing for high temperature superconductivity in the bismuthate . Bismuth and its
compounds are diamagnetic , which limits the Tc of Ba0.6K0.4BiO3 to about 30 K .
Suppose we intercalated layers of a strongly antiferromagnetic copper(II) oxide
compound between layers of the bismuthate perovskite . Would they induce an
antiparallel ordering into its metallic bond free electrons , thereby permitting them to
form much stronger Cooper pairs ? In a sense this has already been accomplished in
BSCCO-2212 , with its alternating layers of partially oxidized Sr2Bi2O5 and Ca2Cu3O5
(refer to the sketch of BSCCO-2212 above) .

Lanthanum copper(II) oxide , mentioned above in connection with Bednorz and


Müller's breakthrough discoveries in 1986–87 , could be examined for this application
. The layered composite from the combination of equimolar quantities of Ba0.6K0.4BiO3
and La2CuO4 , Ba0.6K0.4La2BiCuO7 , might have the following crystal structure :
The syntheses of La2CuO4 , La2NiO4 , and La2CoO4 were first reported in 1960 by
French researchers . La2NiO4 has the K2NiF4 crystal structure , while La2CuO4 and
La2CoO4 have distorted variants of it . In particular , La2CuO4 was tetragonally
distorted ; that is , its copper(II) atoms have a “4+2 distorted octahedral” [tetragonal]
coordination by the oxygen , with four short Cu–O bonds in the x-y plane , and two
longer vertical Cu–O bonds . This tetragonal distortion is caused by the Jahn-Teller
effect , which is ever-present in copper(II) compounds :
This molecular model was based on the sketch by B.M. Klein et al. .

As mentioned above , Arjomand and Machin prepared La2CuO4 and thought it might
be antiferromagnetic :

“La2CuO4 has a very low magnetic susceptibility ........ which remains relatively
constant over the temperature range 8–300 K . It is not clear why this behaviour
occurs , unless there is a very strong antiferromagnetic interaction” (p. 1064) .

They also prepared La2NiO4 in another study of ternary nickel oxides , and similarly
found it to be antiferromagnetic . For typical high spin Ni2+, µ eff ~ 3.1 BM ; at 300 K ,
they found µ eff = 1.70 BM ; at 80 K , they found µ eff = 1.09 BM (Table 3 , p. 1057) .

“Although there is no direct indication of antiferromagnetism [in La2NiO4] , these


observations suggest that such an interaction does occur below 80 K . Compounds
with the K2NiF4 structure are commonly antiferromagnetic” (p. 1057) .

Bednorz and Müller's success with Ba- and Sr-doped La2CuO4 resulted in it being
extensively studied from the late 1980s onward . La2CuO4 , La2NiO4 , and La2CoO4
are now recognized as being quite strongly antiferromagnetic , with Néel temperatures
of around 350 K , 330 K , and 270 K respectively (mentioned by Blundell et al. ,
PDF , 116 KB ; but see the refs. in Several investigations for various different TN
values . Magnetic susceptibilty and TN are very sensitive to the sample preparation
history and to the compound's stoichiometry) .

Several investigations of how partially oxidizing La2CuO4 and La2NiO4 affects their
magnetic susceptibilty and TN are very pertinent to this present report . It was
generally found that partial oxidation of the copper(II) and nickel(II) in the
compounds substantially degraded their antiferromagnetism , flattening their magnetic
susceptibility curves and lowering their TNs . This should come as no surprise in light
of the above discussion of mixed-valent compounds . Partial oxidation is chemically
creating mixed-valent Cu(II)–Cu(III) and Ni(II)–Ni(III) ; the 3d valence electrons in
the Cu(II) and Ni(II) , previously pinned in the homovalent compounds , are now
resonating in the mixed-valent materials . This electron resonance is degrading the
antiferromagnetic ordering of the 3d electrons in the lattice .

We can now clearly see the dilemma of high temperature superconductivity : on the
one hand , we need the Robin-Day Class II (Class 3) mixed-valent resonance to unpin
the valence electrons in the homovalent insulators and create a bilayer metallic bond
in them ; but on the other hand , such a resonance destroys the antiferromagnetism we
need to ensure the free electrons have the antiparallel orientation they require for
magnetic coupling into Cooper pairs . Chemists trying to synthesize such
superconductors must therefore find the precise balance between optimizing the
mixed-valency and yet retaining sufficient antiferromagnetism in the modified
material . We will always be confronted by this dilemma as long as we try to design a
superconductor by creating a Robin-Day Class II mixed-valent metallic compound
within an antiferromagnetic homovalent precursor .

However , we might be able to avoid the dilemma by intercalating layers of an


antiferromagnetic induction agent between layers of all sorts of metallic substrates .
For high temperature superconductor candidates any substrate with a bilayer metallic
bond is still preferred , for the reasons outlined above . Electrical conductivity and
superconductivity can first be optimized in that layer if a mixed-valent compound is
the selected substrate . Then , layers of La2CuO4 or La2NiO4 (depending on the
system's redox chemistry) can be intercalated between layers of the metallic solid .

Antiferromagnetism is optimized in stoichiometric La2CuO4 or La2NiO4 , that is ,


neither partially oxidized nor reduced , so researchers should prepare in advance
samples of pure , stoichiometric La2CuO4 or La2NiO4 . They should carry out the
intercalation reactions in an atmosphere of pure , dry argon or nitrogen to avoid any
partial oxidation of the Cu(II) or Ni(II) . Also , the La2CuO4 composites should not be
overheated ; Foëx and co-workers (French researchers) discovered that above 1200 ºC
copper(II) oxidizes some of the oxides to oxygen , and La2CuO4 is converted into a
mixture of La2O3 and Cu2O (Arjomand and Machin prepared CuAlO2 by heating CuO
– not Cu2O – and Al2O3 at 1100ºC for five days) . A moderate reaction temperature of
~ 800–900 ºC for the preparations is therefore recommended . On the other hand ,
La2NiO4 is thermally stable , and can be melted at 1750 ºC without decomposition .
These redox reactions occur (or not) because Cu(II) is a natural oxidizer , with E0red =
0.153 V to Cu(I) , while Ni(II) is a low energy redox species , neither oxidizing nor
reducing in nature .

While copper(II) is resistant to the Bi(V) in Ba0.6K0.4BiO3 , nickel(II) can be oxidized


(at 1.17 V) to nickel(III) by Bi(V) , at ~1.8 V . Therefore , La2CuO4 could be tried as
an antiferromagnetic induction agent with Ba0.6K0.4BiO3 , while La2NiO4 would be
unsuitable for this application .

Wells has pointed out the similarity of the K2NiF4 crystal structure with that of the
perovskites :

“The structure of a number of complex oxides X2YO4 is closely related to the


perovskite structure , which is that of the corresponding oxide XYO3” (p. 499) .

Layers of La2CuO4 should thus be able to intercalate smoothly with alternating


perovskite layers of the mixed-valent bismuthate to form the new composite
La2Ba0.6K0.4BiCuO7 . If the antiferromagnetic induction model is valid , this latter
material should have a substantially enhanced Tc compared to the original
Ba0.6K0.4BiO3 .

Referring to the Table of Oxidizers above , we note that cobalt(II) oxide can't be
oxidized by Bi(V) , so La2CoO4 could also be tried as an antiferromagnetic induction
agent with Ba0.6K0.4BiO3 . Yamada and co-workers measured TN = 275 K for
La2CoO4 .

Normally , researchers would carefully avoid the inclusion of high spin cations with
any superconductor material or candidate . However , they should remember that high
spin copper(II) is found in BSCCO-2212 , for example . I pointed out in the Doping
web page that in the YBCO series of cuprates , MBa2Cu3O7 , superconductivity was
still observed even when M was a paramagnetic Rare Earth cation such as Dy3+, 4f9 ;
Gd3+, 4f7 ; Sm3+, 4f5 ; and Nd3+, 4f3 . These are all inert spectator cations , nested
between the electronically active CuO2 sheets and CuO3 pyramids . The Rare Earth
cations in the YBCO series are off to the side and don't participate in the Cu–O
bilayer metallic bond in them . Their f electron Curie paramagnetism is undoubtedly
much weaker than the d electron antiferromagnetism in the copper(II) cations . They
therefore don't disrupt the formation of the Cooper pairs and are quite innocuous .
Similarly , the layers of La2CuO4 intercalated between the bismuthate layers – in
which the electronic activity actually occurs – shouldn't interfere with the Bi–O
superconductivity , so long as their Cu2+ doesn't mix into the bismuth layers . The two
different layers are somewhat like “oil and water”, and probably would remain cleanly
separated , like the complex layers in BSCCO-2212 .

A second mixed-valent triad that would be interesting to investigate in this new


context is the titanium trio , Ti3+–Ti4+–Ti3+ , which is 3d1– 3d0– 3d1 electronically .
Verwey studied this titanium system in his pioneering research with mixed-valent
compounds and the controlled valence technique of synthesizing them . The electrical
conductivity of strontium titanate rose dramatically from 10-7 ohm-1cm-1 to 0.6 ohm-
1
cm-1 when doped with 1% lanthanum(III) .

Three decades later Johnston prepared a series of Li1+xTi2-xO4 spinel compounds (x = 0


to 0.33) , studying their electrical conductivities from 0–300 K . Superconductivity
was optimized at Tc ~ 13.7 K in the x = 0 compound , LiTi2O4 . Its valence counting
formula , Li 1+ Ti3+ Ti4+ O8-4 , reveals the presence of the Ti3+–Ti4+–Ti3+ triad in the
material . LiTi2O4 was a mediocre semiconductor with a normal state electrical
conductivity of about 10 ohm-1cm-1 , a value which remained remarkably level from Tc
to 300 K [Johnston's Fig. 5 , p. 158] .

Titanium(III) compounds are mildly reducing , so La2NiO4 and La2CoO4 would be


compatible with them (but not the oxidizing La2CuO4) . Electrical conductivity and
superconductivity in Verwey's SrTiO3 – LaTiO3 mixed perovskites would first be
optimized . LaTiO3 , described as “black , slightly iridescent crystals”, is a metallic
solid (Rao) that supplies free electrons to the metallic bond in the Sr–La composites .
It would be doped into the non-metallic substrate SrTiO3 , a cubic perovskite , at
various mole ratios to obtain a series of composites for testing :

x LaTiO3 + (1– x) SrTiO3 ----------> Lax Sr1-xTiO3 ; x = 0 to 1 .

The titanium triad would be present in this system in the composition La0.67Sr0.33TiO3 ,
although that might not be the optimum formula . The optimized LaxSr1-xTiO3 would
then be combined with an equimolar quantity of stoichiometric La2NiO4 to obtain the
layered La/Sr–Ti–Ni–O structure , which hopefully would have a significantly
enhanced superconducting transition temperature relative to the original LaxSr1-xTiO3 .
N. Bergeal and co-workers recently reported that epitaxial films of LaxSr1-xTiO3 they
prepared had a Tc ~ 0.3 K (PDF , 1592 KB) .

The superconducting properties of a third group of mixed-valent compounds , the


tungsten bronzes (and possibly other bronzes , such as the molybdenum bronzes)
might also benefit from the presence in them of an antiferromagnetic induction agent .
Some tungsten bronzes have the cubic perovskite structure while others have related
non-cubic forms . They can be thought of as the insertion of zerovalent metal atoms
into the tungsten trioxide precursor structure . The metal atoms donate their valence
electrons to the WO3 , but rather than reducing it to tungsten metal , the electrons enter
the oxide's frontier orbitals and create a metallic bond XO in the crystal . The inserted
metal atoms remain as electronically inert spectator cations nested in periodic cavities
in the lattice .

The tungsten (and other) bronzes are brightly coloured with a metallic luster , and
they can have high electrical conductivities . For example , the cubic bronze
Na0.85WO3 has an ambient conductivity of around 70,000 ohm-1cm-1 . Despite these
remarkably high conductivities , few of the tungsten (or other) bronzes become
superconducting , even near Absolute Zero . Matthias and co-workers studied the
electrical conductivity near Absolute Zero of a dark blue sample of tungsten bronze
having the approximate composition Na0.3WO3 , whose Tc ~ 0.57 K (onset) .
Rubidium tungsten bronzes have the highest transition temperatures of the alkali
metal tungsten bronzes , with the Tc = 1.98 K for RbxWO3 (x = 0.27–0.29) reported in
1965 . An efficient synthesis of rubidium tungsten bronzes in a microwave furnace
was recently described by J. Guo and co-workers . All the conductive bronzes display
Pauli paramagnetism , with no evidence of any antiferromagnetism .

The mixed-valent triad in the tungsten bronzes is W(V)–W(VI)–W(V) , which is 5d1–


5d0– 5d1 electronically . Tungsten(VI) in the parent material , WO3 , is a very mild
oxidizer [Table of Oxidizers above] , so as with the titanium triad only La2NiO4 and
La2CoO4 could be combined with them for the preparation of new high Tc
superconductor candidates . Apparently the tungsten bronzes , with their bright ,
lustrous colours , are used industrially in paint pigments (Microsoft Word document ,
259 KB) , but I was unable to locate any of their commercial suppliers .

Tungsten bronzes were first prepared in 1823 by the prominent German chemist
Friedrich Wöhler (1800–1882) , and several synthesis routes to them have been
developed since then . In a typical procedure described in detail in Inorganic
Syntheses , W(0) and W(VI) are reproportionated to mixed-valent W(V,VI) using a
mixture of tungsten metal powder , tungsten trioxide , and sodium tungstate salt . This
classical method was recently modernized by carrying it out in a microwave furnace .
Another interesting preparation of a barium tungsten bronze was published by Conroy
and Yokokawa :

x BaCl2 + x WO2 + WO3 ---- (900 ºC , 15 hrs , in vacuo) ------> BaxWO3 + x WO2Cl2
(g) .

The by-product WO2Cl2 was sublimed from the mixture , thus driving the reaction to
completion . However , this resulted in a deplorable loss of valuable metal reagent
from the system . Here's a suggestion for a simple route to sodium tungsten bronzes ,
also involving the evolution of a gaseous by-product – but an expendable one – and
using only relatively inexpensive reagents :

x NaH + WO3 ---- (warm in a stream of pure flowing nitrogen) ------> NaxWO3 + ½ x
H2 (g) ; and ,

x NaBH4 + WO3 ---- (pure flowing nitrogen) ------> NaxWO3 + ½ x H2 (g) + ½ x B2H6
(g) .

Both sodium hydride and sodium borohydride are well-known reagents in organic
chemistry , the former as a strong but non-nucleophilic base , and the latter as a mild
reducer of numerous organic functional groups . The corresponding lithium and
potassium compounds are also known and are commercially available , but are less
frequently used than the sodium chemicals . Hydride is a remarkably strong reducing
agent , and it should readily transfer one of its 1s2 valence electrons to the mildly-
oxidizing W(VI) in the WO3 :

2 W(VI) + 2e- -------------> 2 W(V) ............ E0red = 0.26 V ;

2 H1- – 2e- -------------> H2 (g) ............ E0ox = 2.23 V ;

Net : 2 W(VI) + 2 H1- -------------> 2 W(V) + H2 (g) ............ E0T = 2.49 V

The substantial E0T suggests that the NaH–WO3 reaction could be strongly exoergic ,
so the two compounds should not be compressed into a pellet , but rather gently
mixed together as loose powders . Caution : please take the appropriate safety
precautions if attempting these reactions ! Use of eye protection (safety glasses , with
goggles or a visor) is obligatory , and a safety screen and leather gloves are strongly
advised . Only semi-micro quantities of the reagents (no more than a gram or two)
should be combined in exploratory work , until the researcher is confident that the
reaction – if successful , of course – can be safely scaled up to a preparative level .

The powerful base potassium hydride , KH , is now available in the form of a 50 : 50


blend with solid paraffin wax . In this form it is very stable and easy to manipulate ,
with no loss of its basic properties (PDF , 35 KB) . KH-paraffin could be very useful
in the synthesis of KxWO3 , where the paraffin might dilute down the KH , and so
moderate the addition reaction .

Borohydride isn't as strong a reducer (1.24 V in alkaline aqueous media) as hydride


anion , but NaBH4 is easier to handle than NaH (although it's somewhat hygroscopic ,
which can be a nuisance on those humid summer days) . Aldrich supplies NaH in a
dry powder form (95% pure) , which is more convenient than the mineral oil
dispersions of the Alkali metal hydrides commonly available commercially . The
tungsten bronzes are chemically quite robust , so the reaction products can be
thoroughly washed with water or even dilute mineral acid to remove excess alkali and
water-soluble sodium tungstate impurities without harming the bronze .

The tungsten triad would be represented in the bronze [Na1+]2 [W(V)O3 –W(VI)O3 –
W(V)O3] ; dividing by 3 , we have Na0.67WO3 , which is in the “mid-range” of
sodium-doped WO3 . This may or may not represent the optimum doping level for
superconductor candidates , so I would suggest adding a less doped bronze , say
Na0.35WO3 , and a more highly doped one , say the conductive cubic bronze Na0.85WO3
mentioned above , to the research study of these materials . These three sodium
tungsten bronzes would then be combined with an equimolar quantity of La2NiO4 to
produce the composites La2NaxNiWO7 (x = 0.35 , 0.67 , and 0.85) for physical
testing . A “shake-'n-bake” technique , with an inert atmosphere of pure , dry argon ,
and moderate baking temperatures (~ 800–900 ºC) , would be used in their
preparation . Chemical bonding in La2NiO4 is entirely ionic in nature , while the W–O
bonds in the bronzes are covalent , so hopefully the W–O and Ni–O layers would
remain completely separated in the new W–O–Ni composites .

Molybdenum trioxide , a pale green powder , m.p. 795 ºC , could similarly be reacted
with NaH and/or NaBH4 to produce the corresponding sodium molybdenum bronzes .
The molybdenum triad is 4d1– 4d0– 4d1 for Mo(V)–Mo(VI)–Mo(V) , and the exact
triad would be present in the bronze Na0.67MoO3 [tetragonal K0.5MoO3 has an
unusually high Tc = 4.2 K (Sleight and co-workers)] . MoO3 is somewhat more
strongly oxidizing [Mo(VI) / Mo(V) ~ 0.7 V] than WO3 . It might therefore be
possible to try the more oxidizing La2CuO4 , as well as La2NiO4 and La2CoO4 , as
antiferromagnetic induction agents with the NaxMoO3 bronzes .

Rhenium trioxide , briefly discussed above , would also provide an excellent test of
the antiferromagnetic induction theory . As mentioned earlier , although it has a
remarkably high ambient electrical conductivity , it never becomes superconducting .
It's really a type of bronze , with a cubic crystal structure similar to the tungsten
bronze perovskites [hexagonal K0.3ReO3 has a Tc = 3.6 K (Sleight and co-workers)] .
Its Re(VI) is 5d1 electronically . Rhenium trioxide has a bilayer Re–O metallic bond ,
but it displays Pauli paramagnetism and isn't antiferromagnetic at all . ReO3 could be
layered with an equimolar quantity of La2NiO4 to form the composite La2NiReO7 ,
whose electrical properties would be carefully studied and compared with those of the
parent compound .

The tin triad , Sn(IV)–Sn(II)–Sn(IV) , which is 5s0–5s2–5s0 electronically , would also


be interesting to study in this context . A well-known cubic perovskite , BaSnO3 ,
would provide Sn(IV) . Tin(III) is found in the metallic rocksalt SnP , whose cubic
form superconducts at Tc ~ 2.8–4.8 K . Sn(III) might be stabilized in the compound
LaSnO3 , which could be a metallic perovskite . The series of Ba1-x Lax SnO3
composites could be prepared in the following one-pot reaction :

(1–x) BaCO3 + ½ x La2O3 + ½x SnO + (1– ½x) SnO2 --------- (flowing argon)
--------->

Ba1-x Lax SnO3 + (1–x) CO2 (g) [or ¼x Sn0 + (1– ¼x) SnO2] , where x = 0 to 1 ,

and their electrical conductivities determined . The composite Ba0.33 La0.67 SnO3 [i.e.
3–4–3 , which is equivalent to 4–2–4] would represent the tin triad , although it might
not be optimized with respect to electrical conductivity and superconductivity (if
any) . Tin(II) is very easily oxidized to tin(IV) [0.151 V] , so all of the synthesis
procedures should be carried out in an inert (argon) atmosphere . The optimum Ba1-x
Lax SnO3 composite would then be intercalated with stoichiometric La2NiO4 and/or
La2CoO4 (but not with the oxidizing La2CuO4) to obtain Ba/La–Sn–O–Ni/Co layered
structures for further electrical testing .

The layering of antiferromagnetic induction compounds with metallic solids could be


a very general sort of chemical process , leading to the production of many
remarkable new systems to investigate as potential superconductor candidates . For
example , graphite is a fairly good electrical conductor (about 25,000 ohm-1cm-1 for
virgin , undoped graphite at room temperature) . Its conductivity can be dramatically
increased by the reaction with it of both electron donors and acceptors . The
intercalation compound of graphite with 75% by weight of SbF5 (an electrophilic
acceptor) has the astonishing ambient conductivity of around one million ohm-1cm-1 ,
which I believe is the world record for room temperature electrical conductivity .
Could layers of an antiferromagnetic induction agent be added to this material to
make it an ambient superconductor ?

Another example is titanium disulfide , TiS2 , which I've discussed in the Layered web
page . It has a lamellar morphology like that of graphite , with a golden-yellow colour
and a metallic luster . Its ambient electrical conductivity is about 1400 ohm-1cm-1 , and
while it has an inverse temperature–conductivity relationship , TiS2 apparently never
becomes superconducting , although many of its intercalation products do (but only
close to Absolute Zero) . Suppose a layer of an antiferromagnetic induction agent was
intercalated between each layer of TiS2 ; would the composite then become
superconducting at an appreciable Tc ? Here's a suggestion : equimolar quantities of
TiS2 and the compound tetrakis(triethylphosphite)nickel(0) , [(EtO)3P]4Ni , both of
which are commercially available , could be reacted together . After distillation of the
complexing (EtO)3P ligands from the solid , the nickel atoms would bond with the
sulfurs to form a coating of NiS over the TiS2 layers . Nickel(II) sulfide is known to be
a fairly strong antiferromagnetic material [TN = 263 K (–10 ºC) , Table above] , so
possibly the nickel-intercalated product TiS2Ni might prove to be a superconductor ,
with a Tc well above Absolute Zero .

Combinations of antiferromagnetic induction agents with the wide array of available


metallic solids (with a compatible redox chemistry between the two combining
materials being carefully respected , of course) could in theory provide an large host
of superconductor candidates , and many interesting new materials generally , for
investigation . If supported by experimental evidence , the antiferromagnetic induction
model of high temperature superconductivity would give chemists the ability and
confidence to assume a leadership role in future superconductivity research , in
partnership with solid state physicists , crystallographers , materials scientists , and
technologists .

The study of AFM induction in layers of metallic solids continues in the web page ,
“New Layered Compounds for High Temperature Superconductivity”, with more
examples of metallic–AFM composites .

References , Notes , and Further Reading

mathematical treatise : J. Bardeen , L. N. Cooper , and J. R. Schrieffer , “Microscopic


Theory of Superconductivity”, Phys. Rev. 106 (1) , pp. 162-164 (1957) ; idem ,
“Theory of Superconductivity”, Phys. Rev. 108 (5) , pp. 1175-1205 (1957) .

Matthias's Rules : B.T. Matthias , “Empirical Relation between Superconductivity and


the Number of Valence Electrons per Atom”, Phys. Rev. 97 (1) , pp. 74-76 (1955) ;
see Fig. 3 , p. 75 for a graph of several A15 compounds ; B. T. Matthias , T. H.
Geballe , and V. B. Compton , “Superconductivity”, Rev. Mod. Phys. 35 (1) , pp. 1-22
(1963) ; see Table IV , p. 12 for a list of superconducting A15 compounds . For an
interesting biographical article about Matthias , see : T.H. Geballe and J.K. Hulm ,
“Bernd Theodor Matthias” (unknown source , undated , PDF , 153 KB) . Matthias's
Rules are mentioned on pp. 249-251 .

Simon and Smith's book : R. Simon and A. Smith , Superconductors , Conquering


Technology’s New Frontier , Plenum Press , New York , 1988 ; the A15 crystal
structure sketch is on p. 115 . Note that the labeling of the A and B atoms has been
erroneously reversed in this drawing , i.e. it shows A2B6 (2 x AB3) instead of the
correct A6B2 (2 x A3B) . Matthias's Rules are discussed on pp. 112-114 .
refined and broadened : W.E. Pickett , “Probing Room Temperature
Superconductivity in a Parallel , Wiser Universe . Metaphysical Considerations” (PDF
, 893 KB) , p. 3 (no date) ; idem , “Electron–Phonon Coupling : When Conventional
Becomes Unconventional” (PDF , 8633 KB) ; p. 16 (August , 2009) .

was achieved : J.R. Gavaler , “Superconductivity in Nb–Ge Films Above 22 K”, Appl.
Phys. Lett. 23 (8) , pp. 480-482 (1973) . Matthias had also investigated Nb3Ge earlier :
B.T. Matthias et al. , “Superconductivity of Nb3Ge”, Phys. Rev. 139 (5A) , pp.
A1501-A1503 (1965) . They found that for a bulk sample of stoichiometric Nb3Ge the
Tc ~ 17 K (onset) .

Krebs summed up : H. Krebs , “Superconductivity in Metals , Alloys ,


Semiconductors , and Glasses as a Result of Particular Bond Systems”, Prog. Solid
State Chem. 9 , pp. 269-296 , Pergamon Press , Oxford , UK , 1975 ; pp. 294-295 .
Also in Krebs's textbook : idem , Fundamentals of Inorganic Crystal Chemistry ,
transl. by P.H.L. Walter , McGraw-Hill , London , UK , 1968 ; pp. 231-232 .

diamond : Y. Takano et al. , “Superconductivity in Diamond Thin Films Well Above


Liquid Helium Temperature”, Appl. Physics Lett. 85 (14) , pp. 2851-2853 (2004) ; K.-
W. Lee and W.E. Pickett , “Superconductivity in Boron-Doped Diamond”, Phys. Rev.
Lett. 93 (23) , 237003 (2004) ; E.A. Ekimov et al. , “Superconductivity in Diamond”,
Nature 428 (6982) , pp. 542-545 (2004) . This last paper can be downloaded for free ,
PDF (279 KB) .

Arjomand and Machin : M. Arjomand and D. J. Machin , “Oxide Chemistry . Part II .


Ternary Oxides Containing Copper in Oxidation States-I , -II , -III , and -IV”, J.
Chem. Soc. Dalton Trans. 1975 (11) , pp. 1061-1066 ; Table 3 , p. 1062 .

non-metallic : P. Ganguly and C.N.R. Rao , “Electron Transport Properties of


Transition Metal Oxide Systems with the K2NiF4 Structure”, Mater. Res. Bull. 8 (4) ,
pp. 405-412 (1973) . The electrical conductivity of La2CuO4 is discussed on pp. 408-
409 , and is shown in Fig. 3 , p. 408 . It remains fairly constant (at about 5 ohm-1cm1)
over a wide temperature range (125–1000 K) . I would call it a semiconductor . I
suspect that a very pure sample of La2CuO4 prepared in an inert atmosphere and
completely devoid of any Cu(III) impurity would indeed be an insulator . For example
, very pure NiO is a green insulator , but commercial NiO is a black semiconductor
containing some Ni(III) impurity , thus making it a mixed-valent compound . Okajima
, Yamada , and Yamaya (Several investigations , below) state , “....... La2CuO4 .........
with no excess oxygen is an antiferromagnetic insulator with a Néel temperature TN of
315 K” (p. 1319) .
Bednorz and Müller : J.G. Bednorz and K.A. Müller , “Possible High Tc
Superconductivity in the Ba–La–Cu–O System”, Z. Phys. B64 (2) , pp. 189-193
(1986) .

Several months later : J.G. Bednorz , K.A. Müller , and M. Takashige ,


“Superconductivity in Alkaline Earth-Substituted La2CuO4-y”, Science 236 (4797) ,
pp. 73-75 (April , 1987) . The following report was published three months earlier :
R.J. Cava , R.B. van Dover , B. Batlogg , and E.A. Reitman , “Bulk Superconductivity
at 36 K in La1.8Sr0.2CuO4”, Phys. Rev. Lett. 58 (4) , pp. 408-410 (January , 1987) .

Chu and Wu : M.K. Wu et al. , “Superconductivity at 93 K in a New Mixed-Phase Y–


Ba–Cu–O Compound System at Ambient Pressure”, Phys. Rev. Lett. 58 (9) , pp. 908-
910 (1987) .

frantic search : R.M. Hazen , The Breakthrough , The Race for the
Superconductor , Summit Books , New York , 1988 . See also : B. Schechter , The
Path of No Resistance , The Story of the Revolution in Superconductivity , Simon and
Schuster , New York , 1989 ; J.L. Mayo , Superconductivity , The Threshold of a New
Technology , TAB Books , Blue Ridge Summit (PA) , 1988 ; J. Langone ,
Superconductors , The New Alchemy , Contemporary Books , Chicago (IL) , 1989 ;
Simon and Smith (see above) also provide a good account (“Breakthrough” , Ch. 13 ,
pp. 247-265) of the world-wide research efforts in the high temperature
superconductivity of the cuprates around 1986–87 .

Fermi-Dirac distribution : A.R. Mackintosh , “The Fermi Surface of Metals”,


Scientific American 209 (1) , pp. 110-120 (July , 1963) . The electron theory of metals
is discussed by W.J. Moore , Seven Solid States , An Introduction to the Chemistry
and Physics of Solids , W.A. Benjamin , New York , 1967 ; Ch. 2 , “Gold”, pp. 41-
72 ; see Fig. 2.4 , p. 49 for a sketch of a typical Fermi-Dirac distribution curve .

strength of the covalent bond : R.T. Sanderson , Inorganic Chemistry , Reinhold


Publishing , New York , 1967 ; p. 142 .

G. Vidali : G. Vidali , Superconductivity : The Next Revolution ? , Cambridge


University Press , Cambridge (UK) , 1993 .

wide-ranging survey : M.B. Robin and P. Day , “Mixed Valence Chemistry – A


Survey and Classification”, Adv. Inorg. Chem. Radiochem. 10 , pp. 247-422 , H.J.
Emeléus and A.G. Sharpe (eds.) , Academic Press , New York , 1967 ; see also : P.
Day , “Mixed Valence Chemistry and Metal Chain Compounds”, pp. 191-214 in
Mixed-Valence Compounds : Theory and Applications in Chemistry , Physics ,
Geology , and Biology , D.B. Brown (ed.) , NATO Advanced Study Institute , Series
C , Mathematical and Physical Sciences Series no. 58 , Reidel-Holland (Kluwer
Academic Publications , Hingham , MA) , 1980 ; P. Day , “Les Composés à Valence
Mixte”, La Recherche 12 (120) , pp. 304-311 (mars 1981) ; A.J. Markwell , “Mixed-
Valency Compounds”, Educ. Chem. 25 (1) , pp. 15-17 (January , 1988) . I've
discussed the four Robin-Day classes in my web page , “New Solar Cells from
Mixed-Valent Compounds”, with various examples of each class , and illustrated with
sketches of the examples .

magnetite : The electronic situation in magnetite is quite complex , and there have
been many studies of it over the past decades . For reviews of the physics and
chemistry of magnetite , see the following two articles : F. Walz , “The Verwey
Transition – A Topical Review”, J. Phys. : Condens. Matter 14 (12) , pp. R285-R340
(2002) ; J. García and J. Subías , “The Verwey Transition – A New Perspective”, J.
Phys. : Condens. Matter 16 (7) , pp. R145-R178 (2004) .

Selenium : V. Johnson and A. Wold , “Crystal Growth and Magnetic Properties of


Compositions in the CoS2 : CoSe2 System”, J. Solid State Chem. 2 (2) , pp. 209-217
(1970) : “ …… Se substitution [in CoS2] introduces strong antiferromagnetic
interactions between cobalt atoms” (p. 216) ; K. Adachi , K. Sato , and M. Takeda ,
“Magnetic Properties of Cobalt and Nickel Dichalcogenide Compounds with Pyrite
Structure”, J. Phys. Soc. Japan 36 (3) , pp. 631-638 (1969) : CoS2 is ferromagnetic ,
CoSe2 is antiferromagnetic .

Tarascon et al. : J.M. Tarascon et al. , “Preparation , Structure , Properties of the


Superconducting Compound Series Bi2Sr2Can-1CunOy with n = 1,2, and 3”, Phys. Rev.
B38 (13) , pp. 8885-8892 (November , 1988) . See also H. Maeda et al. , “A New
High Tc Oxide Superconductor Without a Rare Earth Element”, Jpn. J. Appl. Phys.
(Lett.) 27 (2) , pp. L209-L210 (February , 1988) .

oxidize water : M.F. Yan et al. , “Water Interaction with the Superconducting
YBa2Cu3O7 Phase”, Appl. Phys. Lett. 51 (7) , pp. 532-534 (1987) .

Cox : P.A. Cox , Transition Metal Oxides , An Introduction to Their Electronic


Structure and Properties , Clarendon Press , Oxford (UK) , 1995 ; electron
superexchange is discussed on pp. 148-153 , and is illustrated in Figs. 3.21 (p. 150) ,
3.22 (p. 151) , and 3.33 (p. 152) . See also A. Tressaud and J.M. Dance ,
“Ferrimagnetic Fluorides”, Adv. Inorg. Chem. Radiochem. 20 , pp. 133-188 ; H.J.
Emeléus and A.G. Sharpe (eds.) , Academic Press , New York , 1977 ; electron
superexchange is discussed on pp. 136-142 , and is illustrated in Fig. 1 , p. 137 .

bismuthate superconductor : R.J. Cava et al. , “Superconductivity Near 30 K Without


Copper : The Ba0.6K0.4BiO3 Perovskite”, Nature 332 (6167) , pp. 814-816 (1988) ; L.F.
Mattheis , E.M. Gyorgy , and D.W. Johnson , Jr. , “Superconductivity Above 20 K in
the Ba–K–Bi–O System”, Phys. Rev. B37 (7) , pp. 3745-3746 (1988) ; J.J. Krajewski ,
“Synthesis of Superconducting Oxides”, pp. 192-201 in Inorg. Synth. 30 ,
Nonmolecular Solids , D.W. Murphy and L.V. Interrante (eds.) , John Wiley , New
York , 1995 ; the preparation of Ba1-xKxBiO3 is described on pp. 198-199 ; J.C. Stark
et al. , “The Preparation of BaBiO3 and the Superconductor K0.4Ba0.6BiO3 from Mixed
Metal Alkoxide Precursors”, Mater. Res. Bull. 26 (7) , pp. 623-630 (1991) .

French researchers : M. Foëx , A. Mancheron , and M. Liné , “Sur une Combinaison


du Sesquioxyde de Lanthane avec le Protoxyde de Nickel” , Comptes Rendus 250
(18) , pp. 3027-3028 (1960) .

B.M. Klein et al. : B.M. Klein et al. , “Electronic Structure and High Critical
Temperature in Oxide Superconductors”, Ch. 3 , pp. 26-43 in Chemistry of High-
Temperature Superconductors II , D.L. Nelson and T.F. George (eds.) , ACS
Symposium Series 377 , American Chemical Society , Washington , DC , 1988 ;
Figure 1 , p. 28 ; ibid. , J. DiCarlo et al. , “Determination of the Homogeneity Range
of La2CuO4”, Ch. 11 , pp. 140-144 ; Figure 2 , p. 144 . The La2CuO4 structure was
also sketched by J.B. Goodenough , “Ceramic Superconductors , Single-Valent versus
Mixed-Valent Oxides”, Ch. 16 , pp. 287-321 in Electron Transfer Biology and the
Solid State , Inorganic Compounds with Unusual Properties , M.K. Johnson et al.
(eds.) , Adv. Chem. Series 226 , American Chemical Society , Washington , D.C. ,
1990 ; Fig. 15 , p. 318 .

ternary nickel oxides : M. Arjomand and D. J. Machin , “Oxide Chemistry . Part I .


Ternary Oxides Containing Nickel in Oxidation States II , III , and IV”, J. Chem. Soc.
Dalton Trans. 1975 (11) , pp. 1055-1061 .

Several investigations : Y. Okajima , M. Yamada , and K. Yamaya , “Magnetic


Properties of La2CuO4 with Slight Amounts of Excess Oxygen”, Physica C 282-287 ,
Part 3 , pp. 1319-1320 (1997) ; J. Saylor et al. , “Néel Temperature of Stoichiometric
La2CuO4”, Phys. Rev. B40 (10) , pp. 6854-6861 (1989) : “The most significant result
of our work is the conclusion that stoichiometric La2CuO4 has the highest TN [317 K] ”
(p. 6860) ; J. Shimizu , M. Nakagawa , and Y. Oda , “The Normal State Magnetic
Susceptibility of La2CuO4+d with Excess Oxygen”, Physica C 388-389 , pp. 263-264
(2003) ; P. Gopalan et al. , “Influence of Oxygen Stoichiometry on the
Antiferromagnetic Ordering of Single Crystals of La2NiO4+d”, Phys. Rev. B45 (1) , pp.
249-255 (1992) ; R.A.M. Ram , P. Ganguly , C.N.R. Rao , and J.M. Honig ,
“Preparation and Characterization of La2CoO4+δ ”, Mater. Res. Bull. 23 (4) , pp. 501-
506 (1988) . These latter researchers reported a broad TN ~ 150 K for partially-
oxidized La2CoO4 ; stoichiometric La2CoO4 has a TN = 275 K (Yamada and co-
workers , below) . It's noteworthy that in none of these physics-related papers is the
chemistry subject of mixed-valence cations , compounds or resonance ever mentioned
; an unfortunate oversight , in my opinion .

Wells : A.F. Wells , Structural Inorganic Chemistry , 3rd edition , Clarendon Press ,
Oxford (UK) , 1962 . The K2NiF4 structure is sketched in Fig. 166 , p. 499 .

Yamada and co-workers : K. Yamada et al. , “Successive Antiferromagnetic Phase


Transitions in Single-Crystal La2CoO4”, Phys. Rev. B39 (4) , pp. 2336-2343 (1989) .

Verwey : E.J.W. Verwey , “Valence Induite”, Bull. Soc. Chim. France , mises au
point D122 (1949) [“Induced Valence”, Chem. Abs. 43 , 6015g (1949)] .

Johnston : D.C. Johnston , “Superconducting and Normal State Properties of Li1+xTi2-


xO4 Spinel Compounds . I . Preparation , Crystallography , Superconducting Properties
, Electrical Resistivity , Dielectric Behaviour , and Magnetic Susceptibility”, J. Low
Temp. Physics 25 (1&2) , pp. 145-175 (1976) .

iridescent crystals : M. Kestigan and R. Ward , “The Preparation of Lanthanum


Titanium Oxide , LaTiO3”, J. Amer. Chem. Soc. 76 (23) , p. 6027 (1954) .

Rao : C.N.R. Rao , “Localized Versus Collective Behaviour of d-Electrons in


Transition Metal Oxide Systems of Perovskite Structure”, J. Indian Chem. Soc. 51
(12) , pp. 979-987 (1974) ; see Figure 3 , p. 982 .

tungsten bronzes : P.G. Dickens and M.S. Whittingham , “The Tungsten Bronzes and
Related Compounds”, Quart. Rev. 22 (1) , pp. 30-44 (1968) ; H.R. Shanks , P.H.
Sidles , and G.C. Danielson , “Electrical Properties of the Tungsten Bronzes”, Ch. 22 ,
pp. 237-245 in Nonstoichiometric Compounds , R. Ward (ed.) , Adv. Chem. Series 39
, American Chemical Society , Washington , D.C. 1963 ; M.J. Sienko , “Electric and
Magnetic Properties of the Tungsten and Vanadium Bronzes”, Ch. 21 , pp. 224-236 in
Nonstoichiometric Compounds ; C.T. Hauck , A. Wold , and E. Banks , “Sodium
Tungsten Bronzes”, pp. 153-158 in Inorg. Synth. 12 , R.W. Parry (ed.) , McGraw-
Hill , New York , 1970 [republished by R.E. Krieger , Huntington , NY] .

ambient conductivity : Shanks , Sidles , and Danielson in Nonstoichiometric


Compounds (immediately above) ; Fig. 2 , p. 240 .

Matthias and co-workers : Ch. J. Raub et al. , “Superconductivity of Sodium Tungsten


Bronzes” , Phys. Rev. Lett. 13 (25) , pp. 746-747 (1964) ; N. N. Garif'yanov et al. ,
“Superconductivity of Sodium Tungsten Bronze with Cubic Structure”, Czech. J.
Phys. 46 (suppl. S2) , pp. 855-856 (1996) . They reported a maximum T ~ 1.7 K for
Na0.15WO3 .

Rubidium tungsten bronzes : A.R. Sweedler , Ch. J. Raub , and B.T. Matthias ,
“Superconductivity of the Alkali Tungsten Bronzes”, Phys. Lett. 15 (2) , pp. 108-109
(1965) ; R.K. Stanley , R.C. Morris , and W.G. Moulton , “Conduction Properties of
the Hexagonal Tungsten Bronze , RbxWO3”, Phys. Rev. B20 (5) , pp. 1903-1914
(1979) .

J. Guo and co-workers : J. Guo et al. , “Crystal Structure and Superconductivity of


Rubidium Tungsten Bronzes RbxWO3 Prepared by a Hybrid Microwave Method”,
Mater. Res. Bull. 43 (4) , pp. 779-786 (2008) . They reported a maximum T = 5.3 K
(onset) for Rb0.14WO3 .

Inorganic Syntheses : Hauck , Wold , and Banks , “Sodium Tungsten Bronzes”, in


tungsten bronzes above .

microwave furnace : J. Guo et al. , “A Green Route for Microwave Synthesis of


Sodium Tungsten Bronzes NaxWO3 (0<x<1)”, J. Solid State Chem. 178 (1) , pp. 58-63
(2005) .

Conroy and Yokokawa : L.E. Conroy and T. Yokokawa , “The Preparation and
Properties of a Barium Tungsten Bronze”, Inorg. Chem. 4 (7) , pp. 994-996 (1965) .

reagents in organic chemistry : L. F. Fieser and M. Fieser , Reagents for Organic


Syntheses , vol. 1 , John Wiley , New York , 1967 . NaH , pp. 1075-1081 ; NaBH4 ,
pp. 1049-1055 .

Sleight and co-workers : A.W. Sleight , T.A. Bither , and P.E. Bierstedt ,
“Superconducting Oxides of Rhenium and Molybdenum with Tungsten Bronze Type
Structures”, Solid State Commun. 7 (2) , pp. 299-300 (1969) .

SnP : P.C. Donohue , “The Synthesis , Structure , and Superconducting Properties of


New High-Pressure Forms of Tin Phosphide”, Inorg. Chem. 9 (2) , pp. 335-337
(1970) .

intercalation compound of graphite : J.-M. Lalancette and J. Lafontaine ,


“Intercalation of Antimony Pentafluoride in the Lattice of Graphite”, J.C.S. Chem.
Commun. 1973 , p. 815 ; J.-M. Lalancette , “Graphite Intercalated Antimony
Pentafluoride”, U.S. Patent 3950262 , April 13 , 1976 ; F.L. Vogel , “The Electrical
Conductivity of Graphite Intercalated with Superacid Fluorides : Experiments with
Antimony Pentafluoride”, J. Mater. Sci. 12 (5) , pp. 982-986 (1977) ; idem ,
“Intercalation Compounds of Graphite”, pp. 261-279 in W.E. Hatfield (ed.) ,
Molecular Metals , Plenum Press , New York , 1979 ; see especially Table III ,
“Acceptor Intercalated Compounds of Graphite”, p. 269 ; idem , “Process for
Conducting Electricity Utilizing a Specifically Defined Graphite Intercalation
Compound ”, U.S. Patent 4293450 , October 6 , 1981 ; P.G. Rodewald , “Graphite
Intercalation”, U.S. Patent 4035434 , July 12 , 1977 (see especially examples 3 and
4) .

tetrakis(triethylphosphite)nickel(0) : the zerovalent Ni compound


tetracarbonylnickel(0) , Ni(CO)4 , might also be tried in the reaction , but it's a very
toxic , volatile (b.p. 43 ºC) , thermally unstable chemical .
Tetrakis(triethylphosphite)nickel(0) is a stable solid (m.p. ~106 ºC) , and is easier and
safer to handle than Ni(CO)4 . Other zerovalent Transition metal (M) carbonyls could
be reacted with TiS2 to deposit layers of MS in the flakes . For example , Cr(CO)6
(stable , m.p. ~154 ºC) , should deposit CrS , which is strongly antiferromagnetic [TN
= 460 K (187 ºC)] . Pentacarbonyliron(0) , Fe(CO)5 [stable but air-sensitive , b.p. 103
ºC , not as toxic as Ni(CO)4] , should deposit antiferromagnetic FeS [TN = 428 K (155
ºC) ; T. Takahashi , “Magnetic Properties of Stoichiometric Iron Sulfide Single
Crystals near the Alpha Transition Temperature”, Solid State Commun. 13 (9) , pp.
1335-1337 (1973)] . Graphite could be treated with Fe(CO)5 , then exposed to air or
even pure oxygen to leave a deposit of Fe2O3 [TN = 948 K (675 ºC)] on the surfaces of
the flakes . The iron(III) oxide layers might induce superconduction in the graphite at
an elevated transition temperature .

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