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How Solids Melt: ORNL
Simulations Support Theory
By Mark Mostoller, Ted Kaplan, and Kun Chen
Mark Mostoller (right), Ted Kaplan, and Kun
Chen (sitting) view a computer visualization of
two-dimensional melting based on their
computer simulation using ORNLs Intel
Paragon XP/S 35. Photograph by Tom
Cerniglio.
Chocolate melts in our mouths, but
how it turns from solid to liquid isnt
clear in our minds. Recently, three
ORNL researchers have used the Intel
Paragon XP/S 35 to help confirm a
theory developed in the 1970s about
how substances melt in two
dimensions. They simulated two-
dimensional systems containing 576,
4,096, 16,384, 36,864, and 102,400
atoms with an interatomic force model
often used for rare-gas solids. Results
for the two largest systems show the
existence of a new hexatic phase
between the solid and liquid phases, as
predicted by the theory. This two-
dimensional simulation helps explain
the melting process.
Every solid melts if taken to a high enough temperature. For example, hydrogen melts at about
14 Kelvin (or K, the number of degrees above absolute zero); ice at 273 K, iron at 1810 K, and
tungsten at nearly 3700 K, making it very useful as the filament material in light bulbs. Melting in
three dimensions (3D), or the conversion from solid to liquid, is a first-order phase transition in
which a latent heat must be provided. Thus, ice keeps a drink cold by taking in its latent heat, which
causes the ice gradually to melt.
Melting is a fundamental phenomenon that all of us have witnessed and think we understand, but,
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paradoxically, there is no generally accepted picture of how solids melt at an atomistic level.
Instead, there are empirical rules such as the Lindemann criterion, named after the man who
presented it 85 years ago. The atoms in a crystal vibrate around fixed positions, just like a guitar
string when plucked. The size, or amplitude, of the vibrations increases with increasing temperature.
According to the Lindemann criterion, a crystal will melt when the vibrational amplitudes of its
constituent atoms reach some critical magnitude, say 10 to 15% of the interatomic spacing.
Physics is a search for the elegance and simplicity that underlie natures often apparently chaotic
and complex behavior. The Lindemann picture of melting is simple, but it certainly is not elegant. It
proposes that the disorganized vibrations of the atoms in a solid somehow cause the solid to melt at
a very precise temperature. Other phase transitions do not occur in such a disorganized fashion.
Superconductivity, for example, occurs because electrons with opposite spins form pairs that can
move through the lattice without resistance. A number of famous physicists, including Richard
Feynman, have proposed theories for melting in 3D that involved more efficient mechanisms to
mediate the process, but none of these theories has proven true.
In two dimensions (2D), the situation is different. In the 1970s, an elegant theory for melting was
developed by John Kosterlitz, David Thouless, Burt Halperin, David Nelson, and Peter Young (the
KTHNY theory, after the initials of its authors last names). Many experiments and computer
simulations have since been done to prove or disprove the theory, with ambivalent results. The
experiments have often been quite imaginative. They have used layers of rare gas on graphite,
charged polystyrene spheres in solution, and monolayers of metal spheres (metal shot to hunters)
shaken between confining plates. Experimental results generally have been supportive of the
KTHNY theory. In contrast, simulations, in which complications such as interactions of rare gas
atoms with the graphite substrate can be avoided by studying ideal 2D systems, have given
predominantly negative results. A number of people, including Burt Halperin and David Nelson,
thought the reason for these results could lie in the system sizes and time scales employed in the
simulations.
Enter ORNL
Here our part of the story begins. In 1992, the Intel Paragon XP/S 150 became a promise that
would soon be funded. Mark Mostoller and Ted Kaplan began an effort in numerical simulations,
hoping to harness the power the new machine would provide. They persuaded a close friend of
long standing, Mark Rasolt, to join them in this new venture. Rasolt was a very creative and
productive theorist who periodically spent time at Harvard University, where Halperin and Nelson
are professors. Rasolt saw the development of our new capabilities in simulations and the arrival of
the Paragon as an opportunity to test the KTHNY theory at the required system sizes and time
scales for the first time. He also thought that if the mechanism for 2D melting could be confirmed,
the studies could be extended to melting in 3D.
Together we prepared a proposal to the Laboratory Directed Research and Development Program
which Rasolt presented in September 1992. Everyone acknowledged that the proposal carried a
high risk of failure because it would use a then nonexistent machine to examine a fundamental
problem that great physicists had been unable to solve. In November 1992, shortly after learning
that the project had been funded, Rasolt died of a massive heart attack at Los Angeles International
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Fig. 1. A cartoon picture of the order present in the solid,
hexatic, and liquid phases in two dimensions.
Airport while returning from a conference in Australia. He was 49 years old.
It was hard to continue the work then, and it is hard to tell the story now. Kaplan took over
leadership of the project. In August 1993, Kun Chen joined us as a postdoctoral researcher. The
Intel Paragon XP/S 35 came on line in April 1994, and the XP/S 150 began operation in January
1995. Our tools had arrived, and we set to work.
Theoretically Speaking
A principal feature of the KTHNY
theory of melting is its prediction of a
new phase between solid and liquid. A
crystalline solid has two kinds of order,
translational and orientational.
Translational order means that, if you
start at a particular atom and take steps
along well-defined paths over long
distances, you will arrive in close
proximity to another atom. Orientational
order means that, if you look at two
atoms separated by large distances,
their neighbors will be oriented relative
to some fixed axis in the same way. A
liquid has no long-range order of either
kind, but it has short-range order: any
atom will have some average number of nearest neighbors clustered around an average neighbor
distance with no preferred orientation. KTHNYs new phase, called the hexatic phase, has no
translational order but retains orientational order. In short, you cant predict where the atoms are,
but you can predict their neighbor environment.
Figure 1 shows a cartoon representation of the three phases. The theory predicts that under certain
conditions, the system will transform from solid to hexatic to liquid in two continuous phase
transitions that do not involve a latent heat. All of these predictions rest on a picture that invokes
specific defects (dislocations and disclinations) rather than the action of all atoms vibrating willy-
nilly.
Perfected Method for the Paragon
What have we done that is new? Heres the list.
1. We chose to do our simulations with a recently perfected method for treating a constant
pressure (P) and temperature (T) statistical ensemble. A constant volume and temperature
ensemble allows mixed solid and liquid phases that can mimic the hexatic and confuse
analysis. The constraint of constant volume can also cause a problem when equilibrating the
system because vacancies cannot be introduced freely.
2. We chose a longer interaction range for the interatomic potentials than previous simulations.
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For present purposes, this is a detail, but an important one.
3. Our use of the Paragon supercomputer was the real key to our success. Chen has simulated
systems of 576, 4096, 16,384, 36,864, and 102,400 atoms at very long time scales, making
him one of the largest users of the new massively parallel processing machines. To give an
idea of the computer usage involved, a run of 5 million time steps for the 36,864-atom
system at a given P and T takes about 10.5 days running continuously, using 128 nodes on
the XP/S 35.
These were our innovations and computational advantages. Our results provide the strongest
evidence yet that the KTHNY theory of 2D melting is valid. In small samples like those treated in
previous work, we found ambiguous evidence for a first-order transition buried in fluctuations larger
than the transition itself. It was not until the system size reached 36,864 atoms that a metastable
hexatic phase emerged. This phase lasted for about a million time steps before relaxing down into a
liquid. The metastable hexatic phase persists for longer times (3 million time steps) in the larger
102,400-atom system.
Conclusions
We concluded that previous simulations were performed on systems that are too small and that they
were carried out over time scales that are too short. The Paragon and our own insights have made
it possible to find confirmation of a theory for 2D melting. Our research was supported by ORNLs
Laboratory Directed Research and Development Program and reported in Melting in Two-
Dimensional Lennard-Jones Systems: Observation of a Metastable Hexatic Phase, Physical
Review Letters 74, 4019 (1995). For this paper, we received a Lockheed Martin Awards Night
publication award.
Whats left to do? Create a visualization of the 2D melting process at the atomic level and add a
dimension so we can understand 3D melting.
Whats the problem? Getting enough Paragon time.
Whats the lesson? National laboratories that have managers who will take risks can continue to
solve fundamental problems.
BIOGRAPHICAL SKETCHES
MARK MOSTOLLOER was born in Somerset, Pennsylvania, and grew up
in Pittsburgh. He received his Ph.D. degree in applied physics from Harvard
University. He was a staff member in ORNLs Solid State Division from
1969 until spring 1997. He has worked on lattice vibrations, random alloys,
electronic and vibrational properties at surfaces and interfaces, and
numerical simulations of the structure and properties of materials. He
received Martin Marietta technical achievement awards in 1990 and 1992
and a Lockheed Martin publication award in 1995.
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TED KAPLAN is a theoretical physicist in ORNLs Computer Science and
Mathematics Division. Born in New York City, he received both his
undergraduate and Ph.D. degrees from the Massachusetts Institute of
Technology. He has been at ORNL since 1972, when he joined the Solid
State Division. His research has included the theory of random alloys,
fractal interfaces, chaos, rapid solidification, and thin film growth. Most
recently, he has worked on large-scale numerical simulations of the
properties of materials. He received a Lockheed Martin publication award
in 1995.
KUN CHEN, a native of Xiamen, China, was a postdoctoral researcher in
the Solid State Division at ORNL from August 1993 to August 1996. He
received his B.S. degree from Beijing University and his M.S. degree from
Xiamen University. After teaching at Xiamen for 2 years, he came to the
United States in 1988 and received his Ph.D. degree from the University of
Georgia in 1993. He received a Lockheed Martin publication award in 1995.

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