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Development of Novel Materials through Computational Materials Design

(CMD(R))

Article in ECS Transactions · October 2013

DOI: 10.1149/05337.0001ecst

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 Development Novel Materials through Computational Materials Design (CMD®)

H. Kasaia,b , S. M. Asperaa, and A. G. Saputroa

a
Department of Applied Physics, Osaka University, Suita, Osaka 565-0871, Japan
b
Center for Atomic and Molecular Technologies, Osaka University, 2-1
Yamadaoka, Suita, Osaka 565-0871,Japan

COMPUTATIONAL MATERIALS DESIGN (CMD®) has been

proven to be a powerful tool to develop novel materials that suites
the necessities of modern technological advancement. In this
article, the development of CMD® through time will be discussed
as exemplified by different quantum calculations that served as a
benchmark for materials design. Some relevant findings and
applications that have been fully realized with the aid of
methodologies incorporated in CMD® will also be discussed.

Introduction

The relevance of materials, as opposed to machines, in modern technological

advancements has gradually been recognized throughout this modern era as devices
points to more powerful yet smaller in size. Gradually, these are being realized through
the development of nanotechnology. These entail improvement in the functionalities of
materials through design, i.e. materials design. The importance of technological
achievements in materials design can be observed in different fields, such as in
telecommunication, transportation, harnessing alternative energy, education, medicine,
etc., and is evident in our everyday modern living. Recognizing the impact of these
technologies to our society dictates the direction towards which of the research fields
have to be given emphasis.

Significant research in order to be fully realized needs to be in close

association/collaboration with the industry and is dictated by the foreseen needs of the
society. With the demand for more efficient yet environmentally friendly devices,
engineering the structure of materials becomes inevitable. Several experimental
techniques have been proven to develop innovative materials that could very well suit the
needs of the time. But improvement entails stepping through the boundary of what is
already known to what is still a mystery. Opening the door to the next level of research
makes some of the existing experimental techniques inadequate as scientist leads the way
towards understanding of the different properties of materials at the atomic level. This is
where the essentials of theoretical analysis steps in.

Computational Materials Design

Quantum mechanical analysis entails treating the many electron system of the atom
and uses these interactions to determine the different properties of the material as well as
its behavior upon interaction with other materials, without the use of empirical data (i.e.
data derived from experimental results). The structural concept in behind materials design
has been already employed in the early studies of our group, particularly in model
calculations on molecular interaction with metallic surfaces. In the early studies of model
calculations involving H adsorption on metal surfaces using the simple Hamiltonian
model (1), essential parameters like nearest neighbor transfer matrix element (t) and
Coulomb interaction energy (U) in the substrate, as well as the transfer matrix element
between the adatom and the surface were investigated. Considering these parameters, it
was determined that the interaction between the adatom and the metal surface is of local
character such that the effects are prominent on small surface clusters. Furthermore, the
parameter that affects the H atom’s binding strength, U/ , on the metal surface was
determined, and with that a predictive power to determine what kind of surface material
will provide stronger H-metal surface binding, and in this study it was assumed to be with
transition metal surfaces as oppose to simple metal-like surface. Such method of
materials design was extended to early studies on dissociative chemisorption of H2 on
metal surface (2) wherein, using Hubbard’s second approximation, it was determined that
the value of the critical parameter to determine H2 dissociation, VC, is dependent on the
previously known parameter, U/ , used as a criteria to determine H2 molecule binding
strength in the metal surface. As such, this computational method was shown to be a
powerful technique for materials design where studies were extended on quantum
dynamical calculations on larger molecule’s, such NO, scattering on a metal surface such
as Ag (111) (3). In this study, different parameters were investigated to observe each
effect on the final rotational state distribution of NO scattered from Ag (111) surfaces,
and if the theoretical results could still be improved by varying further the parameters of
the model. From this investigation, results show the importance of the correct value of the
well depth to fit the rotational state of NO to a rigid rotor scattered by a rigid flat surface,
and the weak linear dependence of the rotational state maxima on the incident energy
normal to the surface. Furthermore, improvements on the theoretical description were
suggested to improve by considering surface corrugation. Eventually, with these
benchmark systems, progress in materials design enabled surface science-based reaction
design as sampled by studies on ortho-para hydrogen conversion with the purpose of
increasing conversion yield via molecular orientation (4).

Understanding the behavior of materials in different intended purposes could pave the
way for structural engineering through simulations even before going through expensive
experimental trials. A very important computational technique governed by this is first
principles calculations or Ab Initio Calculations where density functional theory (DFT)
has been proven to be one of its most powerful and used tool, among others. Recent
developments in computational techniques, coupled with the rapid progress in computer
efficiency, make ab-initio/first principles-based COMPUTATIONAL MATERIALS
DESIGN (CMD®) a relevant field in the world of surface science and condensed matter
physics (5). Its impact on industrial research and development is depicted by its
contribution to relevant researches in science and technology. Its application has been
used in wide variety of simulation codes that could very well provide results comparable
with that obtained from experiments. This leads to the development of novel materials in
the field of nanotechnology where advances in material science provide improvement in
areas such as solar cells, nanofibers, sensors and ultralight materials. Some recent
applications of CMD® are on fuel cell technology related to finding potential alternatives
to the very expensive platinum commonly used as a catalyst at the electrodes of the fuel
cell using bio-inspired materials such as porphyrin-based materials (6-17), and other
novel materials(18-25); and studies on the role and advantage of inducing spin
polarization and controlling the dynamics of the reaction partners (26-27).

The CMD® process that is originally developed by our group is shown in Figure 1.
This is considered to be an improvement from the usual way of collaboration between
experimentalists and theorists where most often their relationship is merely to explain the
result of the other. In the CMD® process, basic understanding of a physical system is
obtained by theoretical means, e.g. quantum dynamical calculations and/or first principles
calculations. Equipped with these understanding, parameters that are relevant to the
proposed purpose can be altered so as to obtain a new and functionalized material.
Materials testing will then be done by experimentalist to verify physical feasibility of the
proposed new material. The results obtained from these steps will then be used to further
improve the initially proposed material and/or device another material derived from the
basic understanding obtained from materials design. In this cyclic process, a good
collaboration with experimental investigators will be relevant to provide efficient results.
Development of novel materials will then be a result from theses series of processes.

The Naniwa-series

Modern computational techniques at the quantum level entail appropriate codes that
could very well handle/represent the system. Naniwa-series is among the computational
codes which could be used to treat quantum mechanical systems. The first principles
calculations based on DFT treats the electron system quantum mechanically and nucleus
classically, however, the Naniwa-series treats both electrons and nucleus quantum
mechanically. This is important in cases of hydrogen, lithium, and even, oxygen reaction
and dynamics. The Naniwa-series code could perform quantum dynamics calculation and
is considered as the quantum mechanical version of the classical molecular dynamics
(MD). In general, it could also handle quantum transport and quantum scattering.
Different surface reaction involves interaction of a particle which comes in contact with a
surface. Surface reactions such as dissociative scattering, molecular scattering,
dissociative adsorption, associative adsorption and others can be treated by this code
when quantum effects such as tunneling, diffraction, and electronic excitation does not
play an essential role in the dynamics of the system. Also, the kinetic energy of the
approaching particle must be large enough to ensure that the de Broglie wavelength is
much smaller than the lattice constant of the solid (which is typically in order of a few
Angstrom) so that interference phenomena can be neglected. A typical example is the
hydrogen atom, with translational energy of approximately 20 meV and de Broglie
Wavelength of few Angstrom, where it can be treated as a quantum particle. Relevant
surface reaction entails strong interaction with the approaching particle and the surface.
This strong interaction leads to coupling between the internal degrees-of-freedom like
vibration, rotation and translation between the particles involved in the reaction. This
necessitates the quantum mechanical treatment of the system since these internal degrees-
of-freedom, like vibration, requires quantum description especially when the respective
quanta are large. Naniwa-series could very well treat these kinds of system.

First Principles quantum dynamics calculation done by the Naniwa-series can be

broken down into two main stages:
1. A Density Functional Theory (DFT) based determination of the effective potential
energy (hyper--) surface (PES) governing the reaction (28)
2. a. Naniwa Dynamics: Solution of the corresponding multi-dimensional Schrӧdinger
equation for the reaction described by the above-determined PES based on coupled-
channel method (29,30) and the concept of local reflection matrix (31).
b. Naniwa Statics: The quantum states of an atomic motion (i.e. H, D, and Li atoms)
on the constructed PES can be obtained by solving the three-dimensional Schrӧdinger
equation via the variational method (32-35).

For a more detailed discussions on the basics and application of NANIWA-series, c.f. (36,
37).

Figure 1. The Computational Materials Design (CMD®). The process of designing

material structure employing the technique of CMD® is described in comparison with the
previous method of explaining experimental results.

Acknowledgments

This work was supported in part by JST (Japan Science and Technology Agency) through
ALCA (Advanced Low Carbon Technology Research and Development) Program
“Development of Novel Metal-Air Secondary Battery Based on Fast Oxide Ion
Conductor Nano Thickness Film” and Strategic Japanese-Croatian Cooperative Program
on Materials Science “Theoretical modeling and simulations of the structural, electronic
and dynamical properties of surfaces and nanostructures in materials science research”. It
was also supported in part by MEXT (Ministry of Education, Culture, Sports, Science
and Technology) through the G-COE (Special Coordination Funds for the Global Center
of Excellence) program “Atomically Controlled Fabrication Technology”, Grant-in-Aid
for Scientific Research on Innovative Areas Program (2203-22104008) and Scientific
Research (a) (24246013) and (c) (22510107) programs. Some of the calculations
presented here were performed using the computer facilities at the following institutes:
the super computer centers of Institute of Solid State Physics (ISSP) of the University of
Tokyo and Yukawa Institute for Theoretical Physics (YITP) of Kyoto University, High
Energy Accelerator Research Organization (KEK) under a support of its Large Scale
Simulation Program (No. 12/13-10), Cybermedia center (CMC) of Osaka University and
the National Institute for Fusion Science (NIFS).

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