Modelling and Simulation

in
Materials Science

Dr. Isaac Toda-Caraballo

Modelling & Simulation in Materials Science

• Modelling and Simulation, an overview

• Simulating techniques
• Atomistic Scale Simulations (DFT, Molecular Dynamics)
• Meso-scale simulation: Microstructure evolution (Phase-phield method, Vertex and
others)
• Macro-scale Simulations : Finite Element Method

• Data analysis
• Mathematical tools:
• Regression • MonteCarlo
• Optimization • Statistics

• Multiscale modelling & ICME: Integrated Computational Materials

Engineering
• Fatigue • HEAs • Microstructure in ODS

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Simulating Techniques. Atomistic Simulations

Denstity Functional Theory Molecular Dynamic

approaches approaches

Key:
Description of the energy of a
system

Knowledge of a potential
Resolution of Schrodinger Equation +
Newton Laws

𝐹 =𝑚𝑎 3
Simulating Techniques. Atomistic Simulations
Denstity Functional Theory Molecular Dynamic
approaches approaches

DFT is an approach for the MD assumes that atoms move under

description of ground state the Newton Laws
properties of elements

Atomic numbers

Knowledge of a potential
Resolution of Schrodinger Equation +
Newton Laws

𝐹 =𝑚𝑎 4
Simulating Techniques. Atomistic Simulations
Denstity Functional Theory Molecular Dynamic
approaches approaches

Knowledge of a potential
Resolution of Schrodinger Equation +
Newton Laws

𝐹 =𝑚𝑎 5
Simulating Techniques. Atomistic Simulations
Denstity Functional Theory Molecular Dynamic
approaches approaches

The energy is calculated at each step The energy can be known at each step, but not
• Very time consuming necessarily
• Just a few atoms • Very fast
• Millions of atoms
Static simulation
Forces can be also calculated Forces can be also calculated
• Very, very, very time consuming • Fast
• Just a few atoms can be included in the • Times around 1e-9 s (with steps of 1e-15 s )
simulation & extremely low simulating
times.

Dynamic simulation

Knowledge of a potential
Resolution of Schrodinger Equation +
Newton Laws

𝐹 =𝑚𝑎 6
 Simulating Techniques. Molecular Dynamics

𝐹 =𝑚𝑎 Instead of using Quantum mechanics,

we can use classical Newtonian
mechanics to model our system

10-9 m

10-5 s 10-10 m

10-12 s

This is a simplification of what is

actually going on, and is therefore
less accurate.
.
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Simulating Techniques. Molecular Dynamics

𝐹 =𝑚𝑎
To improve accuracy, calculations from
Quantum Mechanics can be used as input
for classical mechanics.

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Simulating Techniques. Molecular Dynamics
Newton History of Mechanics

Lagrange

Hamilton
𝐹 =𝑚𝑎

𝐿 =𝑇−𝑉 Einstein

𝐻 =𝑇+𝑉

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 Simulating Techniques. Molecular Dynamics

History of Mechanics
𝐹 =𝑚𝑎

The concept of Hamiltonian is used to re-connect

Quantum Mechanics to Classical Mechanics and allow
Molecular Dynamic Simulations

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Simulating Techniques. Molecular Dynamics

Extreme importance of Halmilton Mechanics

𝐹 =𝑚𝑎

Only the correct expression of the Hamiltonian

(Energy of the system) is needed to calculate
evolution from atoms to stars.
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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

The dual atomic nature wave/particle duality, and

can be described by a function called a wave-
function 𝛹(r).

The wavefunction of a particle, 𝛹(r), tells us

what the probability is of finding the particle in a
given region of space.

Where, the probability over all space is 1

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

In materials modelling, the general intention is to know the ground state of a system.
In order to determine the energy of a system we need to apply the energy operator,
called the Hamiltonian H

For a single, free particle the Hamiltonian is very simple since the particle only has
kinetic energy. The kinetic energy operator T is the second derivative of the
wavefunction with respect to the spatial coordinates

Planck’s constant, m is the mass of the particle

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

In general a particle will also have some potential energy and so we need to define a
potential energy operator V. The form of the potential energy operator will vary
depending on the system under consideration, but will often include electrostatic
attraction and repulsion, as well as other terms such as magnetic interactions. Once the
potential energy operator has been found, the Hamiltonian is simply the sum of the
kinetic and potential terms

For systems of many particles the wavefunction gives the probability of finding the
system in a particular state, i.e. particle one in a certain region of volume and particle
two in another certain region of volume and so on. This ‘many-body wavefunction’ is
now a function of the spatial coordinates of all of the particles, and so can become
extremely complicated. However the general properties remain the same, and in
principle the total energy of the system can be found simply by applying the Hamiltonian
and integrating over all space
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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

In the Born–Oppenheimer approximation, the electrons respond instantaneously

to any change in the nuclear configuration. Within this approximation, the nuclei
simply provide an external potential for the electrons, with the energy due to the
electrostatic interactions between the nuclei determined classically.

electronic kinetic energy, electron–nucleus interaction, the electron–electron interaction

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

The Hohenberg–Kohn Theorem

Hohenberg and Kohn showed that the ground state energy of a set of interacting
electrons in an external potential is a unique functional of their density

where E[n(r)] is the Hohenberg–Kohn energy functional, n(r) is the single-electron

charge density, V(r) is the external potential and F is a unique functional.

charge density n0(r) that minimises E[n(r)] must be the exact ground state density
for the system, and the value of the functional for this density gives the exact
ground state energy.

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

Trial structures

Decreasing formation energies

Composition - XY2

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

Bloch’s Theorem and the Supercell

In a crystal we have an extra symmetry, that of periodicity. This periodicity imposes
a constraint on the charge density, namely that it must be invariant under
translation by a lattice vector

where g is a linear combination of lattice vectors

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Simulating Techniques. Atomistic Simulations
Denstity Functional Theory
approaches

Cluster Expansion Method

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

Assumption:
Atoms behave following Newton´s second law

𝐹 =𝑚𝑎

𝐹= 𝐹𝑖

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

1 Potential 2 Geometry

3 Periodic
Boundary 4 Solver
Conditions

5 Computer

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

Any interatomic potential is the results of adding the atomic repulsive force and the
atomic attractive force

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

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 Simulating Techniques. Molecular Dynamics

Finnis-Sinclair Potentials Sutton-Chen Potentials

Gupta Potentials

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
Finnis-Sinclair Potentials approaches

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
How can a potential be fitted? approaches

Quantum mechanics calculations

Experiments

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
How can a potential be fitted? approaches

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

2 Geometry:
The most important is the set-up
of the model

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches

3 Periodic Boundary Conditions

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Simulating Techniques. Molecular Dynamics
Molecular Dynamic
approaches
4 Solver

NVE: constant number (N), volume (V), and energy (E); the sum of kinetic (KE) and
potential energy (PE) is conserved, T and P are unregulated

NVT: constant number (N), volume (V), and temperature (T); T is regulated via a
thermostat, which typically adds a degree of freedom to the conserved Hamiltonian; E
and P are unregulated

NPT: constant number (N), Pressure (V), and temperature (T)

Ideal gas law

PV=nRT

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Simulating Techniques. Atomistic Simulations

Denstity Functional Theory Molecular Dynamic

approaches approaches

𝐹 =𝑚𝑎

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Simulating Techniques. Atomistic Simulations

Denstity Functional Theory Molecular Dynamic

approaches approaches

CASTEP Materials Studio

Gaussian Discovery Studio
Quantum ESPRESSO GROMACS
Schrodinger CHARMM
SIESTA
VASP LAMMPS

Materials Universe DL_Poly

Medea

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