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University of Virginia
In this lecture we will talk about the computational materials science, a relatively new and one of the fastest
growing disciplines in materials science. We will start from a short discussion of the basic ideas behind
computer simulations and the increasingly important role the simulations play in scientific research in
general and in materials research in particular. Then we will have a short overview of contemporary
computational methods used in design and optimization of new and existing materials, consider a few recent
success stories, and discuss some of the current limitations and challenges faced by the computational
materials science.
From mathematical description to computer simulation
Over the centuries that followed the time of Galileo, the computational work was focused on finding
analytical solutions of the equations that describe the behavior and properties of a system of interest.
Finding analytical solution for complex systems is a very difficult task. In 1929 one of the fathers of
quantum mechanics, Dirac, wrote The underlying physical laws necessary for the mathematical theory of a
large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that
the exact application of these laws leads to equations much too complicated to be soluble.
Indeed, not only the solution of quantum mechanical equations is intractable, except for some special cases,
but the classical mechanics problem of many interacting bodies cannot be solved analytically for more than
3 bodies. Similarly, the equations for the gas/fluid flow, electrical/magnetic fields induced by static or
moving charges, etc. are well known but usually difficult to solve for any conditions of practical interest. In
the situation when analytical solution of the equations is difficult, the invention of computers has provided a
new exciting possibility to solve the complex equations numerically, in a computer simulation. During the
last half century computer modeling has developed into a very powerful method of scientific research used
in almost all areas of science, from biology and economy to nuclear physics and astronomy. The pace of the
development of computational methods and applications of computer simulations was different in different
areas of science, though. The majority of chemical and pharmaceutical companies these days are routinely
using computer simulations of molecular structures and interactions to accelerate the design of new drugs
and chemical compounds. The leading engineering companies, such as Airbus, Boeing, Ford, and GM, are
modeling aerodynamic and mechanical characteristics of aircrafts and automobiles before building physical
models and testing them in a wind tunnel or crashing them into a wall. At the same time, the development
and application of computer modeling in material science was rather slow over the years and only now we
are experiencing a very fast increase in the number and quality of computational studies in materials
research. In order to understand the reasons for the dramatic change in use of simulations in materials
science, we shall consider, first, the specifics of problems that traditional materials science is dealing with
and, second, the drastic increase in the available computational power, resulting from the design of new
computers with multiple processors and special parallel architecture tuned for computationally intensive
calculations. Below we will consider these two factors in more details.
Mesoscopic
10-9
10-12
Atomistic / Nanoscopic
1021
Length Scale, number of atoms
109
103
106
10-3
Length Scale, meters
10-9
10-8
10-7
Macroscopic
r r
m i a i = Fi
or
mi
dv i r
= Fi
dt
or
mi
d ri r
= Fi
dt 2
If the particles of interest are atoms, and if there are a total of Nat of them in the system, the force acting on
the ith atom at a given time can be obtained from the interatomic potential V(r1, r2, r3, , rNat) that, in
r
r
general, is a function of the positions of all the atoms, F = - V( rr , rr , rr ,..., rr )
i
N at
r
F2
Force
r
F1
r r
r12 = r1 r2
Energy
r
r
V(r12 )
F1 = F2 = dr12
-0.005
repulsion
-0.01
2
attraction
4
Once the initial conditions and the interaction potential are defined, the equations of motion can be solved
numerically. The simplest but not very accurate method that can be used to solve the equations is so-called
Eulers method:
r
r
If we know the positions and velocities of all particles in a system at time t, ri (t ), v i (t ) , we can find the
positions and velocities at time t + t:
F(t)
t
m
The result of the solution are the positions and velocities of all the atoms as a function of time.
500 m/s
r
r
r r r
r
Fi = - i V( r1 , r2 , r3 ,..., rN at )
tn+1 = tn + t
ri (t n ) ri (t n +1 )
r
r
vi (t n ) vi (t n +1 )
MD simulation
As we can see from the snapshots from the simulation of droplet collision above, a rather complex behavior
can result from the integration of a set of very simple equations of motion for a group of interacting atoms.
One of the main strengths of the molecular dynamics method is the ability to reproduce fast non-equilibrium
processes with atomic-level resolution (e.g. microscopic mechanisms of damage/plastic deformation due to a
shock wave propagation, dynamic fracture and crack growth, ion or cluster bombardment, etc.). The method
can be also used to study equilibrium thermodynamic properties of the materials under conditions that is
difficult to achieve experimentally. Below we will first discuss the limitations of the molecular dynamics
method and then consider a few examples of application of this technique to materials-related problems.
1. Classical description of interatomic interaction. In a molecular dynamics simulation electrons are not
present explicitly, they are introduced through the potential energy that is a function of atomic positions only
(this is called Born-Oppenheimer approximation in quantum mechanics). The potential energy, in turn, is
approximated by an analytic function that gives the potential energy U as a function of atomic positions. As
you remember, we need the potential energy to calculate forces, that are obtained as a gradient of a potential
energy function. Design of the potential function and choice of the parameters is often based on fitting to
available experimental data (e.g. equilibrium geometry of stable phases, cohesive energy, elastic moduli,
vibrational frequencies, temperatures of the phase transitions, etc.). If the potential is designed based on one
set of properties, it may not work well in the description of other properties that were not included in the
parameterization
2. Classical description of atomic motion. In classical molecular dynamics we replace Schrdinger
equation for nuclei with classical Newton equation. Quantum mechanical analysis suggests that the wave
nature of electrons dominates over the particle behavior, and electrons can not be considered within classical
approximation. At the same time, all atoms, except for the lightest ones such as H, He, Ne, can be
considered as point particles at sufficiently high temperature and classical mechanics can be used to
describe their motion.
3. Time- and length-scale limitations. The fact that in a molecular dynamics simulation we have to
integrate the equations of motion for all atoms in a system puts severe limitations on the number of atoms
that can be included in the simulation and the time of the simulation. These limitations constrain the range
of problems that can be addressed by the method.
Time-scale: The maximum timestep of integration in a molecular dynamics simulation is defined by the
fastest motion in the system. The period of vibrational motion of atoms in a solid is typically on the order of
hundreds femtoseconds (1 fs = 10-15 s) to picoseconds (1 ps = 10-12 s). Therefore, a typical timestep in the
simulation cannot be longer than a femtosecond. Using modern computers it is possible to calculate 106
108 timesteps. Therefore we can only simulate processes that occur within 1 100 ns. This is a serious
limitation for many problems that involve diffusion, cluster/vapor film deposition, relaxation of irradiation
damage, and other processes that occur at a longer time-scale.
Length-scale: The size of the computational cell is limited by the number of atoms that can be included in
the simulation, typically 104 107. This corresponds to the size of the computational cell on the order of
tens of nm. Any structural features of interest and spatial correlation lengths in the simulation should be
smaller than the size of the computational cell. To make sure that the finite size of the computational cell
does not introduce any artifacts into the simulation results, one can perform simulations for systems of
different size and compare the measured properties.
Dealing with the time- and length-scale limitations of the molecular dynamics method
Record time scale protein folding simulation. Simulation of 1 microsecond of folding of a small, 36
amino-acid, protein with surrounding water molecules (12,000 atoms total) took ~3 months of dedicated
computing using all 256 processors of CRAY-T3E supercomputer at Pittsburgh Supercomputer Center.
Timestep of 2 fs was used 1s = 5108 steps of integration.
Record length scale multi-billion simulations of crystal fracture, discussed in the next page.
Due to the limitations on the size of the system that can be simulated, an important aspect of any molecular
dynamics simulation is an adequate description of the interaction of atoms in the system (sometimes called
computational cell) with surrounding infinite material. We have to define boundary conditions and
apply special methods for temperature and pressure control in the molecular dynamics computational
cell (heat and work exchange between the molecular dynamics computational cell and the surroundings).
surface
MD
MD
Large external system
Nano-jet implantation of functional molecules into a polymer substrate [Masahiro Goto et al., J. Appl. Phys.
90, 4755-4760, 2001]
Test run with 5,180,116,000 particles has been performed in 2000 by J. Roth, F. Ghler, and H.-R.. Trebin
[Int. J. Modern Phys. C 11, 317-322, 2000] in Jlich, Germany on 512 processors of Cray-T3E computer.
The test run took 40 minutes for 5 timesteps of integration.
Kinetic Monte Carlo method for simulation of slow thermally-activated processes, such as diffusion.
As you remember from previous lectures, the atomic diffusion
is a thermally-activated process. In the case of the vacancy
diffusion mechanism this means that in order for an atom to
jump into a vacancy site, it needs to overcome a high energy
state, when old bonds are already broken and new ones are not
formed yet. The probability for an atom to get enough energy
for a jump can be described by the Arrhenius equation:
Energy
Em
Atom
Vacancy
Distance
R j = R 0 exp E m
k
T
B
The pictures below show the result from kinetic Monte Carlo
simulation of island growth on a homogeneous substrate and a
substrate with nanoscale patterning.
http://www.lce.hut.fi/publications/annual2000/node22.html
Dislocation Dynamics
As you remember from the lecture on defects, dislocations are linear defects that are responsible for plastic
deformation in crystalline solids. If we understand the dynamics and interaction of dislocations in materials,
we will be able to understand and, ultimately, control the mechanical properties (strength and plasticity) of
materials. The complexity of a collective behavior of a large number of dislocations in crystals undergoing
plastic deformation makes it difficult to provide a complete and consistent theoretical description of plastic
deformation. Mesoscopic simulation method of dislocation dynamics provides additional means for
checking existing theoretical concepts and development of new ideas in this research area.
The dislocation dynamics model is based on the following ideas:
Spatial discretization: The simulated area is grided with grid size that is larger
than the distance of spontaneous annihilation of two dislocations (typically
several nanometers).
Dislocation lines are represented by chains of connected dislocation segments.
New segments are introduced if two adjacent segments become too long (if the
curvature is too crudely described).
Forces acting on dislocations are calculated based on the elasticity theory. These forces include forces due
to the interaction of the elastic fields of different dislocations, external forces of mechanical loading, etc.
Short-range interactions (reactions) of dislocation cores are described based on the results of molecular
dynamics simulations and experimental data.
Equations of motion of dislocations are solved (different methods has been proposed for description of
dislocation motion, including Monte Carlo-type and molecular dynamics type methods).
Below are a few examples of dislocation dynamics simulations:
! An object is divided into small pieces (like in a Lego game) that are called elements. Each element is
defined by nodes.
! A proper behavior is assigned to the elements and physical quantities are defined on each element.
! A system of equations, that describes evolution of quantities in the system of connected elements is
solved.
! Quantities of interest (e.g. stress, strain, density, temperature, etc.) are calculated on each element.
Element
Nodes
To learn more about modeling in materials science, check the web page for MSE 524 course
http://www.people.virginia.edu/~lz2n/mse524/
and take this class.