Simulated Diffusion in a

2 Dimensional Lorentz Fluid

Vale Cofer-Shabica
Richard Stratt, Advisor

Be sure to have a timer in hand at this point. You

have 15 minutes. Speak slowly, clearly.
 Diffusion ???
What is it? Why do we care?

A kind of rate
Reaction Kinetics

Diffusive vs. Ballistic
Catalyst Design
Motion
Semiconductor
“doping”

A kind of rate that tells us about the flux of material as

it moves from a locally concentrated to uniform
distribution

Ballistic vs. Diffusive motion

Most chemical reactions occur in solution. One of the

effects of this is that things get around to happening
at a molecular level only when reactants wander
into each other
 “Slow” Fluids

Honey

Molasses

Magmas and Lava

Glasses

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 The Lorentz Fluid

A randomly
distributed static
field of overlapping,
hard d-Dimensional
Hyper-Spheres

How does this help

us understand slow
liquids?

In the 2D case, a hypersphere is just a circle

Emphasize static spheres

Has many of the the trappings of super-cooled liquids

<> Disordered
<> Phase-transition like behaviour with percolation
(near p=.35)
Explain this via trapping (draw?)
 Geodesic Theory

Diffusion rates are connected to the
shortest path through potential energy
landscapes

Define geodesic of a system: in our case, the

shortest possible path between 2 points

This method was show to be very successful for high

dimension systems (order 1500 degrees of
freedom)
The the 2d Lorentz gas provides us with a very
simple model to try to tease apart what's actually
happening
Reducing complexity enables us to do things like see
this path (point), which we can't visualize as easily
in higher dimensional space
 How do we do experiments on 2D
“liquids” composed of non-
physical particles?

For the record, real experiments are done on 2D

fluids – they're just done on surfaces and at
interfaces
 Molecular Dynamics (MD)
Simulation

Typically, a discrete implementation of
Newton's laws and numeric integration

F = 
U

In our case, a rather large geometry problem

Several problems to work out:

<> Finding collisions
Explain stepping
<> Ballistic collision calculations (angle in, angle out)
<> Multiple object collisions
 Playing Pinball with Lorentz

Lay out the disks

Choose initial
conditions

Solve the geometry
problem

Take measurements

Repeat ~106 times

Average the results
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But what do we measure?

 Diffusion

Two options:
1
D = lim  r t  r 0 2 (Einstein Relation)
t  2dt

2 
v
D =
d
  v 0
v t dt (Green-Kubo Relation)

We're trying to get at diffusion, there are two

equivalent ways we can go

We like one better than the other because integrals

soak up errors whereas derivatives propagate them
 Measurements

Velocity Autocorrelation Functions & Mean Square Displacement
(for now)

C vv t * = v 0
v t *

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Brief description of an autocorrelation function – the

same if it's one, opposite if it's negative one

Point out increasing density

Point out negative regions – a backwards bounce
 Results

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Results are plotted in unit-less quantities by making

comparison to the Boltzmann Free diffusion case

None of the simulations pictured achieved

quantitative agreement with Hofling & Franosch
(2007) at high density
 What Went Right?

Quantitative
agreement in low
density region

Appropriate
qualitative trend with
increasing density

Fixing problems
yielded better
results!

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 What Went Wrong?

Missing obstacles entirely

Step size adjustment

Finite size effect

Periodic boundary conditions

Multiple collision situations*

Particle still fails to become trapped at high
density

Algorithmic adjustments

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 References

McQuarrie (2000)

Hofling & Franosch (2007)

Allen & Tildesley (1987)

Alley (1979)

Bruin (1974)

Special thanks to Bruin for giving me results which, though incorrect, match my own
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 Thanks & Acknowledgements

Rich Stratt

Peter Weber

Crystal Ngyuen

Brian Bayes

My Family & Friends

The Chemistry Department

All of you

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Questions?

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