Materials have played an important role in advancing our civilization.

Search for new and exotic materials has been

the domain of experimentalists for a long time. Using first-principles calculations based on the principles of quantum
mechanics, particularly, the Density Functional Theory, theoretical calculations have enabled the materials scientists
to predict the structure and lattice constants of a material accurately. It is possible to design a material with desired
properties on paper, which has been a long cherished dream of materials scientists.

DESIGNER AND EXOTIC MATERIALS

R. Prasad Department of Physics

Abstract: During the last two decades first-
principles calculations have played an
increasingly important role in the design of
new and exotic materials. This has been
possible due to the rapid development of the
Density functional theory and fast algorithms.
Also increasing power of computers has made
such calculations possible. These calculations
have predictive power and can be used for the
search of new and exotic materials. This article
will give an overview of the role played by such
calculations. After discussing the basic
principles of materials design and some
introduction to the first-principles
calculations, the article will focus on few
selected examples. This will include atomic
clusters, magnetic multilayers and lithiated
manganese oxides, on which work is already in
progress at IIT Kanpur.
1. Introduction
Materials have played an important role in
advancing our civilization. Their importance is
apparent as various periods in our history have
been named after materials such as Stone age,
Bronze age, Iron age and now Silicon age. As
we know silicon and silicon based devices have
changed the way we live. But our search for
new materials has not ended there and still
continues. There is a tremendous amount of
ongoing research for new and exotic materials
such as high Tc superconductors,
nanomaterials, spintronics materials, battery
materials, multiferroics, metamaterials etc.
These materials have potential to produce
technologies which will completely change
our lives.
Search for new and exotic materials has been
the domain of experimentalists for a long
time. However, during the last two decades
theoretical calculations have started playing
an important role. This has been largely due
to the development of first-principles
calculations based on the principles of
quantum mechanics, particularly, the Density
Functional Theory. These calculations use no
adjustable parameters and the only input they
require are atomic numbers and masses of
the constituent atoms. As a result the
structure and lattice constants of a material
can be predicted accurately. Once the
structure is known, the electrical, optical and
magnetic properties can be calculated. Thus it
is possible to design a material with desired
properties on paper, which has been a long
cherished dream of materials scientists.
Fortunately, the computing power has
increased several folds during the last decade
together with rapid progress in the
development of fast algorithms and it is
now possible to do such calculations. Since
experiments are very expensive and time
consuming, such theoretical calculations
could be of immense value in the search for
new and exotic materials. In future, perhaps
such calculations will precede the

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 experimental work on materials design. In this
article I will give a few examples of such
calculations performed at IIT Kanpur.
Properties of a material depend on type of
constituent atoms, atomic arrangement, size
and dimensionality of the material. Thus new
materials can be designed by (i) doping or
alloying (ii) changing structure (iii) changing
size and (iv) dimensionality. For example, a
small doping of boron or phosphorus
impurities in silicon can change its electrical
conductivity by a huge amount and this has led
to the development of silicon based
electronics. Alloying has been used very
effectively in changing the band gaps and is the
basis of band gap engineering. A very good
example of how changing the structure of a
material can change its properties is carbon.
Carbon in diamond structure shows totally
different properties compared to when it is in
graphite structure. Also when a material's size
is less than a nanometer it starts showing
different properties from its bulk form due to
q u a n t u m c o n f i n e m e n t e f f e c t s. I t s
dimensionality also affects its properties i.e. a
material in a thin wire form (1 d) or in thin sheet
form (2d) can show very different properties
from its bulk form. Understanding correlations
between these parameters and properties is key
to designing new and exotic materials.
The plan of this article is as follows. In Section
2, I shall give a brief introduction to first-
principles calculations and their limitations. In
Section 3-5, I shall discuss how such
computations can be used to design (i) atomic
clusters (ii) magnetic multilayers and (iii) a
stable phase of LiMnO2 for cathode material in
rechargeable batteries.
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2. First-principles Calculations
The first- principles calculations are based on
the principles of quantum mechanics and do
not have any adjustable parameters. The only
input quantities are atomic numbers and
masses of constituent atoms. The method is
accurate and can make predictions regarding
structure and material properties.
The most popular first-principles methods are
based on the Density functional theory
(DFT)[1]. The density functional theory deals
with the problem of interacting electrons. In
density functional theory the basic quantity is
the density of electrons and not the many body
electron wave function. The DFT essentially
reduces the many body problem to one body
problem. Using this theory, the ground state
energy can be calculated very accurately. By
optimizing ground state energy, it is possible to
determine atomic arrangement, structure,
elastic constants, transport, magnetic
properties etc. For developing this theory
Walter Kohn was awarded the Nobel Prize in
1998.
A very important development in this field
occurred in 1985 when Car and Parrinello
showed how first-principles molecular
dynamics can be done by combining the DFT
with statistical mechanics[2]. By using this
method one could predict the structure of a
material , predict its vibrational spectrum and
calculate finite temperature properties such as
melting point and specific heat.
The first-principle calculations have many
limitations at present. The method is
computationally very expensive. It can deal
with only order of few thousand atoms with geometry of a large number of clusters have
present computers. However, infinite solid can been studied. As an example, in Fig. 1, we show
be handled using the periodic boundary the ground state structure of Si5 cluster and
condition. This limits the length scales to the how it grows due to addition of hydrogen[3].
order of 100 A. Also time scales are very small
-12
of the order 10 s. It also uses approximations
such as the local density approximations or the
generalized gradient approximations, which
may do very poorly when applied to some
materials such as strongly correlated systems.
However, in spite of these limitations, the
method has proven very useful in designing
new materials.

3. Atomic Clusters

Atomic clusters are finite aggregates of atoms

containing a few to several thousands atoms.
Atomic clusters can have very different
properties from isolated atoms or bulk material
and thus can be considered to constitute a new
type of material. The electronic, magnetic,
optical and chemical properties of these
clusters have been found to be very different
from their bulk form and depend sensitively on
their size, shape and composition. Highly
stable clusters have been designed which can
act as building blocks or basis to form a cluster
assembled solid. These developments are
adding new frontiers to material science and
offer possibilities of designing new materials
with desirable properties by assembling
suitably chosen clusters.
Since many cluster properties such as geometry
and structure of a cluster are not directly
measurable from experiments, theoretical
models and the first-principles calculations
play important roles in the study of clusters.
Using the Car-Parrinello method, structure and
Fig. 1. Evolution of Si5 cluster with hydrogenation .
The bigger circle s are Si and dark dots are H.
As the cluster grows it undergoes significant
rearrangements and reconstructions. Si5 cluster
has a symmetric cage like closed structure
which is a trigonal bipyramid. When hydrogen
is added, the structure of Si5 cage does not
change up to the addition of 3 hydrogen atoms.
But with the addition of 4 hydrogen atoms Si5
cage begins to distort. With 6 hydrogens the
Si5H6 structure is fully saturated as each Si has 4
saturated bonds. We also note that Si5H6 has a
highly symmetric structure. With 7 hydrogen
atoms, the structure of Si5 is completely
changed and takes the shape of a pentagonal
ring. With 10 hydrogen atoms this pentagonal

82
 structure gets fully saturated. With 12 hydrogen
atoms the Si5 structure goes into a more open
structure and results in a symmetric tetrahedral
structure. Thus, we see that addition of
hydrogen atoms can cause drastic changes in
the geometry and structure of Si clusters. In
certain cases even a single impurity atom can
cause a large change in the geometry and
structure of the cluster. This change in
structure can cause drastic changes in chemical
in Fig 3, I show the energy gap between first
excited state and the highest occupied state for
hydrogenated Si clusters as a function of size,
when the number of atoms is small[4]. We see
that the gap fluctuates. But as the number of
atoms in cluster gets larger, the fluctuations
become very small and the gap approaches the
bulk value as shown in Fig 4[5].

FIRST EXCITED ELECTRONIC LEVEL GAP (eV)

FIRST EXCITED ELECTRONIC LEVEL GAP (eV)
properties also. Although these results pertain
to Si clusters, they have relevance for
hydrogenated amorphous silicon and porous
silicon as these systems contain some
hydrogen.

Properties of a cluster depend on its size and

this is schematically shown in Fig 2.

Cluster Property vs Size NUMBER OF SILICON ATOMS

Value of physical property

quantum size Fig. 3. First excited state electronic level gap of Si nH and
effect regime Sin cluster versus number of silicon atoms in the cluster.
The circles and squares correspond to Si nH and Si n clusters
respectively.
ENERGY GAP (eV)

Number of atoms in cluster

Fig.2: A schematic diagram showing change in a
physical property as a function of the size of a cluster

When the size of the cluster is small, say up to

20 or 30 atoms, the value of a physical property
fluctuates with size due to quantum size effect,
but as the size grows and the cluster has a large
NO. OF SILICON ATOMS
number of atoms, the fluctuations get smaller
and eventually it converges to the bulk value. Fig. 4. Energy gap between the first excited state and
Thus by tuning its size, a cluster having the highest filled level in hydrogenated silicon clusters
desired value can be designed. As an example,

83

Note that the method and approximations
used in the calculations shown in Fig. 3 and
Fig.4 on page 83 are different : in the first, the
LDA is used while in the other it is
TDDFT/B3LYP. Nonetheless, the qualitative
nature of the results conforms to the trend
shown in Fig. 2 on page 83.
Clusters can show very large change in its
properties by a slight manipulation in its
structure or its charged state[6,7]. For example,
neutral SiH4 has a very symmetric tetrahedral
structure as shown in Fig. 5.
Fig. 5. Effect of charging on the geometry of SiH 4 and CH4 clusters.
When it is charged, it shows a very large change
in its geometry and has no longer the
tetrahedral symmetry [6]. This is often referred
to as symmetry breaking. Interestingly, SiH4 has
different structures when charged positively
and negatively. This symmetry breaking is due
to the fact that in the distorted structure, the
system lowers its energy by lifting the
degeneracy of electronic levels in the
symmetric structure. This is called the Jahn-
+
Teller effect. Surprisingly, CH4 cluster distorts
+ -
differently from SiH4 but CH4 has the same
+
geometry as CH4 . These surprising results can
be understood very simply in terms of electro
negativities of the constituent atoms and
charge transfer between them[6].
4. Magnetic Multilayers
Magnetic multilayers are artificially designed
materials which have found important
applications in magnetic sensors and magnetic
storage media like computer disks and random
access memories. A typical magnetic multilayer
has several thin layers of magnetic
materials(FM) separated by thin layers of
nonmagnetic material (NM) in a periodic
arrangement as shown schematically in Fig. 6
on page 85.
The magnetic layers can interact magnetically
with interlayer exchange coupling, J. It was
found that the interlayer coupling J shows
damped oscillatory behaviour with the
thickness, d of the nonmagnetic layer as shown
schematically in Fig. 6[8]. This means that
depending on the thickness of the
84

nonmagnetic layer the magnetic layers could
align ferromagnetically or
antiferromagnetically. This was a very
interesting result which provoked a lot of
interest in these materials.
Another interesting result which makes the
magnetic multilayers technologically important
is the large change in their electrical resistance
due to the application of magnetic field and
known as giant magnetoresistance (GMR)[9].
For example Fig. 7 on page 86 shows the
resistance of various Fe-Cr alloys as a function
of applied magnetic field . One notices a large
drop in the resistance as a function of the
applied magnetic field. In the absence of
magnetic field these alloys had
antiferromagnetic arrangement. When the
85
Fig.6. Magnetic Multilayer
and damped oscillations
magnetic field is applied, the
magnetic layers get ferromagnetically aligned
resulting in a large drop in the resistance. It is
the GMR effect of these materials which is
exploited in various applications and started
intense search for materials showing GMR.
The first-principles calculations can be very
useful in the search of magnetic multilayers
showing GMR and interlayer exchange
coupling (IEC). Also these could be used to
explore fundamental issues, such as mechanism
of GMR and IEC. We have tried to explore the
mechanism of IEC in Fe/Nb magnetic
multilayers using the first-principles
calculations [10,11]. There are basically two
prominent theoretical models which have been
proposed to explain IEC; first is known as the

Ruderman-Kittel-Kasuya-Yosida (RKKY)
model and the other, the quantum well (QW)
model. The RKKY interaction stems from the
spin-polarization of the inter vening
conduction electrons in the spacer layer. In the
Quantum Well model, the coupling arises due
to the spin-dependent confinement of
electrons inside the spacer medium as the size
of the multilayer system is reduced to the
nanometer range. By comparing the results of
these models with the results of the first-
principle calculations, it should be possible to
elucidate the mechanism of IEC for this
system.
Fe/Nb is an interesting system to study the
interlayer exchange coupling, in the sense that
Fe is a strong transition-metal ferromagnet
(FM) while the spacer layer can be a
superconductor (SC) at low temperatures.
Thus apart from the phenomena of oscillatory
Fig. 7: Resistance of Fe-Cr
alloys in magnetic field
exchange coupling between FM layers, Fe/Nb
superlattices have another interesting
phenomenon known as the "proximity effect",
which paves the way for new sources of
magneto-resistance with potential applications
in magneto-electronics. The presence of the
internal magnetic field in Fe layers weakens the
phenomena of superconductivity, due to the
breaking of Cooper pairs. Among various
FM/SC hetero-str uctures, where
superconductivity gets induced in the
ferromagnet by bringing it in contact with the
superconductor, Fe/Nb multilayers have been
studied experimentally to an appreciable
extent. Since Nb is the highest known Tc
element, its interplay with Fe continues to
remain an active field in the study of such
heterostructures.
Total energy calculations have been carried out
for Fe/Nb multilayers in the framework of the
86
 linearized-muffin-tin-orbitals method [11]. The bcc Fe layers are stacked along the [001]
Various tetragonal supercells are constructed growth direction in ferromagnetic (FM) as well
out of Fe and Nb monolayers (ML) as shown in as antiferromagnetic (AFM) orientations.
Fig 8.
The interlayer exchange coupling (IEC ), J,
corresponds to the energy difference between
FM and AFM configurations per unit cell
structure. The IEC for Fe/Nb multilayers is
shown in Fig. 9. Rapid oscillations are
observed up to 9 monolayers (ML) of Nb
thickness, after which the oscillatory exchange
coupling becomes appreciably weak. The
Fig. 8: Unit cell of coupling changes from ferromagnetic to
Fe/Nb multilayer antiferromagnetic configuration at about 2, 7
and 10 monolayers of Nb spacer, resulting in
oscillation periods of 7.7 and 4.6 A respectively.
These results were then analyzed to elucidate
the RKKY or QW nature of coupling. Our
analysis indicates that the quantum well model
gives a better description of the oscillatory
behavior of the exchange coupling in Fe/Nb
multilayers.
Exchange
erlayeerr Exchange Couplin
Coupling g (meV)
(meV)

Fig. 9: Interlayer exchange

coupling of Fe/Nb multilayer
with spacer thickness
terlay
InInt

Number of Nb layers

87
5. Lithiated Manganese Oxide: A Battery
Material
At present rechargeable lithium-ion batteries
are the batteries of choice for applications in
portable electronic devices such as mobile
phones and laptop computers. This is because
they offer high energy density, are lightweight
and last longer than other batteries. In these
batteries the charge transport occurs via
lithium ions. At present LiCoO2 is the material
which is used as cathode material. However,
this material is very expensive, toxic and poses
safety problems, and therefore there is a need
for its inexpensive replacement. LiMnO2 could
be a cheap alternative at approximately 1%
cost. There is further incentive to develop this
material for cathode, as India has large reserves
of manganese. Although LiMnO2 is chemically
similar to LiCoO2, it poses several problems.
The stable form of LiMnO2 is orthorhombic
which is less favorable for Li
insertion/extraction cycling than the layered
rhombohedral strucrure of LiCoO2. However,
a metastable form of layered LiMnO2 has been
synthesized but this phase is not stable during
Li insertion/extraction cycles. Thus the
problem of phase stability has to be solved
before this material could be used as a cathode
material.
First-principles calculations could guide the
design of such a material[12-15]. First it has to
be understood, why the rhombohedral phase
(Fig. 10 on page 89) of LiMnO2 becomes
unstable. This is because the oxidation state of
Mn in LiMnO2 is 3+ and it is a Jahn-Teller ion in
the rhombohedral environment. This means
that it will lead to cooperative monoclinic
distortion (Fig. 11 on page 89) which is absent
in LiCoO2. If somehow, the oxidation state of
Mn could be pushed to 4+, such a distortion
could be suppressed as Mn4+ is not a Jahn-
Teller ion. This could be achieved by doping of
certain elements such as Co or Mg at the
manganese site. To find out which dopant
would be most suitable, we have performed the
first-principles calculations of total energy for
pure and doped LiMnO2 in rhombohedral and
monoclinic phases. From these calculations, it
was possible to estimate the concentrations of
dopants, which would be necessary to suppress
monoclinic distortion. These concentrations
are given in Table 1[15]. The table clearly shows
that Mg is the best dopant, as it requires
minimum amount to stabilize the
rhombohedral phase. Further study found that
the divalent dopants, such as Mg and Zn
produce the best results as they force the
neighbouring Mn to 4+ state[14]. It should be
pointed out that the numbers given in Table 1
are rather approximate and perhaps, are on
higher side. This is due to various
approximations used in our calculations which
seem to overestimate the concentration to
s t a b i l i z e t h e r h o m b o h e d r a l p h a s e.
Nevertheless, these calculations could be used
to guide the design of suitable material for
cathode in a lithium-ion battery.
Table 1
Minimum concentrations of dopants
Ni 27%
Co 28%
Fe 32%
Mg 26%
9
88
 Fig.10: Rhombohedral LiMnO 2

Fig.11: Monoclinic LiMnO 2

89
10
References
[1]. P. Hohenberg and W. Kohn, Phys. Rev.
136, B864 (1964).
[2]. R. Car and M. Parrinello, Phys. Rev. Lett.
55, 2471 (1985).
[3]. D. Balamurugan, Ph. D. Thesis, I.I.T
Kanpur (2004).
[4]. D. Balamurugan and R. Prasad, Phys. Rev.
B 64, 205406 (2001).
[5]. C. S. Garoufalis, A. D. Zdetsis and S.
Grimme, Phys. Rev. Lett. 87, 276402 (2001).
[6]. D. Balamurugan, M. K. Harbola and R.
Prasad, Phys. Rev. A 69, 033201 (2004).
[7]. D. Balamurugan and R Prasad, Phys. Rev.
B 73, 235415 (2006).
[8]. S. S. P. Parkin, N. More and K. P. Roche,
Phys. Rev. Lett. 64, 2304 ( 1990).
[9]. M. N. Baibich, J. M. Broto et. al, Phys. Rev.
Lett. 61, 2472 (1988).
[10]. N. N. Shukla and R. Prasad, Phys. Rev.
B70, 014420 (2004).
[11]. N. N. Shukla, A. Sen and R. Prasad, Phys.
Rev. B.(2007).
[12]. R. Prasad, R. Benedek and M. M.
Thackeray, Phys. Rev. B71, 134111 (2005).
[13]. N. N. Shukla and R. Prasad, J. Phys. Chem.
Solids 67,1731 (2006).
[14]. R Prasad, R Benedek et.al, Phys.Rev.B 68,
012101, (2003).
[15]. N. N. Shukla, S. Shukla, R. Prasad and R.
Benedek, (unpublished).

Prof. Rajendra Prasad is a Ph.D from the University of Roorkee, India.

He is a Condensed Matter physicist, whose chief interest lies in the
Electronic structure of disordered systems. Currently, he is working
on hydrogenated silicon clusters, lithiated manganese oxides and
magnetic multilayers. Dr. Prasad is also interested in molecular
dynamics simulations and genetic algorithms..

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