CMD WORKSHOP – OSAKA
August 31 – September 4, 2020

Introductory LectureonComputational Materials Design
Yoshitada Morikawa
Graduate School of Engineering, Osaka University

OUTLINE• Materials Design• Computational Materials Design: CMD®
• History of the CMD® Workshop• First-Principles Calculations• Special Features of the Present CMD® Workshop

CMD® is a registered mark by the CMD® consortium.

Materials Design• Goal of Materials Design- Discovery of novel materials with desired property/function,
generally including optimization of property/function thatknown materials already possess• An Inverse Problem of Realization
REALIZATION
Materials

Direct Problem
Properties

Structure
Composition

Inverse Problem
DESIGN

Functions

Computational Materials Design: CMD®
• CMD® is the theoretical design/optimization of materials withdesired property/function. Specifically, CMD® involves theefficient use of computational techniques to conduct
calculations based on the basic quantum theory.

• Key Developments of Emerging CMD®
- Quantum Theory of Electrons‣ Electronic states governing most of properties (and oftenfunctions) that materials possess- Computational Techniques: Methods, Algorithms, and Codes- High-Performance Computers• The purpose of the CMD® Workshop is to provide thefundamental knowledge and techniques needed to enable
materials design by computations.

先端科学序論I

スーパーコンピューター Top500• ２０１２年１１月共用開始、１０PFLOPS(１京回／秒)

クラス別履修指導

Computer exceeds Human Brain?

• Yes in chess in 1997
• Yes in Japanese chess in 2013
• Yes in games of go in 2016.

Computational Materials Design Workshop• Background- In 2001-2002, a Specialist Training Project was held at theInternational Institute for Advanced Studies (IIAS) in Kyoto, in thefield of Information Biology. — An active effort to not merely
ensure that the students acquired the target knowledge but ratherto create opportunities for bilateral interchange with theinstructors, with the aim of using the synergy to train a group ofspecialists who would become the future leaders in these areas.

- Osaka University had many researchers specializing in firstprinciples calculations: Profs. H. Akai, H. Katayama-Yoshida, H.
Kasai, and so on. They launched the “Development of methods forcomputational nano-materials design” computer-based project
involving some other researchers in Japan under the support ofJST in 2001.

- Through the receipt of assistance from the JST project, the CMD®
Workshop was born in September 2002 as the second IIAS
specialist training project.

1st CMD® Workshop at IIAS in September 2002⇧
Morikawa⇧
Yoshida⇧⇧Akai Kasai⇧
Hamada⇧NakanishiComputational Materials Design Workshop• Since 2002 the 5-day Workshops have been held twice a year
(spring and autumn) and the 33rd Workshop is being witnessed
here.

- Total number of participants (till 32nd WS): 1418
‣ Grad. & Undergrad. Students: 815‣ University/College Staffs (incl. National Labs): 248‣ Industry Researchers: 355

http://phoenix.mp.es.osaka-u.ac.jp/CMD/

Asian CMD® Workshop• Since around 2007, the number of foreigners attending theWorkshop from Southeast Asia has increased. Most of these are
graduate students studying abroad at Osaka University. This
made it difficult to conduct the lectures and hands-on training inJapanese only, and not only the explanatory slides but the oral
explanations came to be presented in both Japanese and English.
This style of instruction has continued to these days, but it has
produced problems as well.

• Interchange with people from the Southeast Asian region throughthe CMD® Workshop became the inspiration in 2008 for the start ofAsian CMD® Workshop in Southeast Asia. In August 2008, the first
Asian CMD® Workshop was held at Institut Teknologi Bandung inIndonesia. In September 2008, an Asian CMD® Workshop was heldat De La Salle University in the Philippines. In the following year,
Asian CMD® Workshops were held again in Indonesia and thePhilippines, and in Vietnam as well. In 2010, the number ofcountries was expanded to four with the addition of Thailand. It
has continued to be held till these days.

4th CMD® Workshop at DLSU in 2011

First-Principles Calculations• Provide a way for solving a direct problem by prediction.

PREDICTION
Materials

Direct Problem
Properties

Structure
Composition

Inverse Problem
DESIGN

FunctionsFirst-Principles Calculations★ Starting from first principles, equations are derived under someapproximations and solved for a realistic system.

★ Two main characteristics:- General-purpose: the methods do not depend on material
systems and properties to be studied- Non-empirical: the methods do not require any experimental
parameters and knowledges as input except for fundamental
physical quantities (m, e, h)‣ We may possibly:
Predict properties to be compared with experimentsUnderstand underlying microscopic mechanisms
Design new materials with desired property/function

First-Principles Calculations• Basic Approximations- Born-Oppenheimer Approx. → Interacting N-electron problem
under external field (nuclear position: structure)- One-electron Approx. → Non-interacting problem‣ Local Density Approximation to Density Functional Theory
Kohn-Sham equations to be solved• Band Theory for Crystalline Systems• Real-Space Methods for Nanostructure Systems

What We Get• Many kinds of physical quantities that can be directly comparedwith experimental observables- Structural properties‣ heat of formation, phonon, elastic constants, thermalexpansion, ...

- Electric properties‣ electric polarization, piezoelectric constants, Born charges,...

- Magnetic properties‣ magnetic moments (spin and orbital), magnetic coupling,magnetoanisotropy energy, hyperfine constants, ...

- Optical properties‣ optical constants, absorption spectra, ...
- .....

Catalysis• Catalyst accelerate chemical reactions byreducing activation barriers but it itself does notchange before and after chemical reactions.
A + Bà

ABEnergy

Without catalyst

With catalyst

Ammonia synthesis• Haber-Bosch process
N2 + 3H2 ⇔Carl BoschThe Nobel Prize inChemistry 1931Fritz Haber
The Nobel Prize inChemistry 1918

NH3 + 46.1 kJ/mol• Iron promoted with K O and Al O （Fe O ・Al O ・K O）• First manufactured using the Haber process on an22

3

34industrial scale in 1913 in Germany• à 80% Fertilizer, plastics, fibers, explosives

232Nobel Prize 2007: Gerhard Ertl

• Contribution to Surface
Chemistry• Elucidate chemical reactions atsolid surfaces in atomic level.

Gerhard Ertl
The Nobel Prize in Chemistry 2007

Suzuki-Miyaura cross coupling

Phenylboronic acid + Bromobenzene→BiphenylPd(Ⅱ)

R1-R2

Pd(0)

R1-X

reductiveelimination
R1-Pd(Ⅱ)-R2• Important in synthesizing

transmetalation

M-X
molecules for liquid crystal
display, organic electroR1,R2 = 芳香族化合物
X = ハロゲン
luminescent devices, and drugs.

oxidative
addition
R1-Pd(Ⅱ)-X
displacement
M-R2

Three way catalyst for Automobil Exhaust Gas• Convert the following three emission gases.
CO+ O2 à CO2NO+ COHC+ O2 à CO2à CO2+ N2+ H2 O• 三元触媒（Three Way Catalyst）• Pt・Rh(10:1)、 Pt・Pd・Rh、 Pd・Rh、 Pdなど
• Rhは資源的に厳しい。
• Pt: South Africa 74%、Russia 14%• Pd: South Africa 25% Russia 70%• Rh: South Africa 67%、Russia 17%

Fuel Cell
Polymer Electrolyte Membrane Fuel CelleH2O

Polymer
Electrolyte

CO poisoning

CathodeH2AnodeH2+à2H+ + 2ePt-Ru

H+½ O2+2H+ + 2e-àH2O
Pt+Fe, Co, Ni
O2

Low Activity

反応の触媒金属依存性

Catalysis• Catalysts are important in not only industries but also inenergy problems and environmental problems.
à It is necessary to design catalysts with abundantelements.
à By elucidating reaction mechanisms, it will be possible
to design new catalysts theoretically.
It is possible to clarify mechanisms of chemical
reactions from first-principles simulations.

O2 Adsorption Energy： Substrate metal dependence

I. Toyoshima and G.A.
Somorjai, Catal. Rev. Sci.
Eng. 19, 105 (1979).

CO Adsorption Energy： Substrate metal dependenceCO Adsorption State： Substrate metal dependence

Dissociate

Molecular

G. Borden, T.N. Rhodin, C. Brukner, R. Benbow,and Z. Hurysh, Surf. Sci. 59, 593 (1976).

Catalytic Activity：Metal dependenceN2 + 3H2

à 2NH3N2 + 2* à 2N(a)H2 + 2* à 2H(a)N(a) + 3H(a) à NH3(a)NH3(a)
à NH3↑

N2Desorption
LimitedN2Dissociation
LimitedCO、N2 Molecular Orbital
N2COLUMO
HOMO

Interaction between MO and d-orbitals• Second order perturbation2V
εd ++V S
εd −εaEFEF

εdεaAdsorbate DOSd-band DOS2V
εa −+V S
εd −εaCO adsorption energy2&)
VπE d −hyb ≈ −4 ( f− fSπ Vπ +' ε 2π −ε d*2&)
Vσ− 2 ((1 − f )− (1+ f ) Sσ Vσ +ε d −εσ'*

B. Hammer, Y. Morikawa, J.K. Norskov, Phys. Rev. Lett., 76, 2141 (1996).

CO adsorption energy

B. Hammer, Y. Morikawa, J.K. Norskov, Phys. Rev. Lett., 76, 2141 (1996).

Molecular adsorption energy2,)
Vπ
Ed − hyb ≈ −4 * f+ fSπ Vπ '+ ε 2π −ε d(2σ,)
V− 2 *(1 − f )+ (1 + f )Sσ Vσ '.
ε d −ε σ+(For late transition metals ( f ≈ 1),2π,)
VEd − hyb ≈ −4 * f+ fSπ Vπ ',+ ε 2π −ε d(2VπδEd − hyb ≈ −4 fδε d .
2(ε 2π −ε d )Adsorption energy VS d-band center
If V is fixed and ed is varied
2πV
δEd − hyb ≈ −4 fδε d .
2(ε 2π −ε d )-3.0-2.5-2.0-1.5-1.0
ed（eV)

M.Mavrikakis, B. Hammer, J.K. Norskov, Phys. Rev. Lett., 81, 2819 (1998).

CO dissociation processCO dissociation process

Y.Morikawa, J.J. Mortensen, B. Hammer, J.K. Norskov, Surf. Sci., 386, 67 (1997).

Adsorption Energy and d-band
center-3.0-2.5 -2.0
ed（eV)-1.5-1.0-3.0-2.5 -2.0

-1.5

-1.0

ed（eV)

M.Mavrikakis, B. Hammer, J.K. Norskov, Phys. Rev. Lett., 81, 2819 (1998).

Universality in Heterogeneous Catalysis

J.K. Norskov et al., J. Catal.
209, 275 (2002).

Hydrogen Evolution Reaction

J. Greeley, T. F. Jaramillo, J. Bonde, I. Chorkendorff, and J.K. Norskov,
Nature Materials, 5, 909 (2006).

Hydrogen Evolution Reaction

J. Greeley, T. F. Jaramillo, J. Bonde, I. Chorkendorff, and J.K. Norskov,Nature Materials, 5, 909 (2006).

Hydrogen Evolution Reaction

J. Greeley, T. F. Jaramillo, J. Bonde, I. Chorkendorff, and J.K. Norskov,
Nature Materials, 5, 909 (2006).

Oxygen Reduction Reaction

J. Greeley, I.E.L. Stephens, A.S. Bondarenko, T.P. Johansson, H.A. Hansen, T. F. Jaramillo, J.
Rossmeisl, I. Chorkendorff, and J.K. Norskov, Nature Chemistry, 1, 552 (2009).

Oxygen Reduction Reaction

J. Greeley, I.E.L. Stephens, A.S. Bondarenko, T.P. Johansson, H.A. Hansen, T. F. Jaramillo, J.
Rossmeisl, I. Chorkendorff, and J.K. Norskov, Nature Chemistry, 1, 552 (2009).

Pt3MoPt3Fe
Pt3Cr
Ni Pt3Co
Pd3Cr
PtMn
3
Pt3Cu
d3Cu
Pd3Ni
Pd3Co

0−2

Pt3Y−4

Pt3Sc

−6

Pt

0.0

Pt

0.2

0.4

0.6

0.8

1.0

U (V) (RHE)

0.00.2b0

j (mA cm−2)

Pd3V

aj (mA cm−2)

NATURECHEMISTRY DOI:Reaction
10.1038/NCHEM.367
OxygenReduction−2

Pt3Y−4showing thePt3Sc−6
Pd skin surface, as
0.00.20.4
0.6
0.8
1.0
rgy of formation ofal precursors,
U (V) (RHE)de results for theof the alloying
Figure 3 | Anodic sweeps of cyclic voltammograms of Pt, Pt3Sc and Pt3Y in
J. Greeley, I.E.L.
Stephens,
A.S. Bondarenko,
T.P. Johansson,
H.A. Hansen,
O2-saturated
electrolyte.
a, The first stablesweep. b, A comparisonof T. F. Jaramillo, J.
en adsorption
Rossmeisl,
I. Chorkendorff,
andJ.K.and
Norskov,
Chemistry,
1, 552 (2009).
the firststeady cycle (solidlines)
after 90 Nature
minutes ofcycling
at of Pt,

30th CMD® Workshop• Beginners Course- Machikaneyama, STATE-Senri, ABCAP• Advanced Course- HiLAPW, feram, Machikaneyama, Naniwa, STATE-Senri• Supercomputer Course- RSPACE• Expert Course• Spintronics Design Course• Lectures- Case Study I–IV
- Special Lecture I-II

Hope you enjoy the Workshop
http://phoenix.mp.es.osaka-u.ac.jp/CMD/