A phase diagram in a jar

One of the things I love about colloids is just how visual they are. Be it watching them jiggling around under a confocal microscope, or the beautiful TEM images of crystal structures, I always find them quite inspirational, or at least instructional, for better understanding statistical mechanics.

Sedimentation

Just to prove I'm on the cutting edge of science, I recently discovered another neat example from 1993. At the liquid matter conference in Vienna Roberto Piazza gave a talk titled "The unbearable heaviness of colloids". As a side note there was a distinct lack of playful titles, maybe people were too nervous at such a big meeting. Anyway, the talk was about sedimentation of colloids.

Sedimentation is something I don't usually like to think about because gravity, as any particle physicist will agree, is a massive pain in the arse. Never-the-less, my experimental colleagues are somewhat stuck with it (well, most of them). As is often the way it turns out you can turn this into a big advantage. What Piazza did, and then others later, was to use the sedimentation profile of a colloidal suspension to get the full equation of state, in fact the full phase diagram, from a single sample.

The nicest example is from Paul Chaikin's lab (now in NYU, then in Princeton), where they used a colloidal suspension that was really close to hard spheres. They mixed a bunch of these tiny snooker balls in suspension, and then let it settle for three months. What they got is this lovely sample, with crystal at the bottom (hence the strange scattering of the light), and then a dense liquid which eventually becomes a low density gas at the top. It's as though the whole phase diagram is laid out before you.

Equation of State

This is a very beautiful illustration, but it's not the best bit. In the same way that atmospheric pressure is due to the weight of the air above you, if you can weigh the colloids above a particular point in the sample then you can calculate the pressure at that point. This is exactly what they did. There are many different ways to measure the density of colloids at a particular height, if you can do it accurately enough (which was the big breakthrough in Piazza's 1993 paper) then you can calculate the density as a function of pressure. In a system where temperature plays no role such as this, this is exactly the equation of state (EoS).

When compared with theoretical calculations for hard spheres the experimental data lies perfectly on the theory curves, complete with first order phase transition where it crystallises. This is really a lovely thing. EoSs are very sensitive to exact details, so in the same way that in my group we compare our simulation of the EoS to check our code, this showed very accurately that their colloids really were hard spheres.

So I think this is all very nice. I nicked the above images from Paul Chaikin's website, I recommend having a poke around, there's loads of great stuff (you really need to see the m&ms).

Colloids are just right

All being good it looks like I've secured employment for a tiny while longer. Hooray!

The place I'm moving to is a big place for synthetic colloids, so it seems like a good time to go through what I know about colloids. If nothing else it'll be interesting to compare this to what I'll know in a year's time! So, here is a theorists perspective on colloid science.

I'll spare the usual introduction about how colloids are ubiquitous in nature, you can go to Wikipedia for that. The type of colloids I'm interested in here are synthetic colloids made in the lab. They're usually made from silica or PMMA (perspex), you can make a lot of them, they can be made so they're roughly the same size and you'll have them floating around in a solution. By playing with the solution you can have them density matched (no gravity) or you can have them sinking/floating depending what you want to study.

The colloids that people make sit nicely in a sweet spot of size and density that make them perfect for testing our fundamental understanding of why matter arranges itself in the way it does. Colloids can undergo most of the same phase transitions that we get in molecular systems, but here we can actually see them. Take for example this beautiful electron microscope image of a colloidal crystal from the Pine group at NYU.

1. They're big enough to image

Colloids are usually of the order a micron across. At this size it is still possible to use confocal microscopy to image the particles. While nothing like the resolution of the electron microscope, the confocal can actually track the positions of individual particles in real time, in solution. It's almost like a simulation without the periodic boundary conditions! A confocal can take lots of 2D slices through the sample, such as below from the Weeks group. The scale bar is 5 microns.

If you do it quick enough then you can keep track of the particle moving before it loses its identity. The Weeks group did some very famous work visualising dynamic heterogeneity in liquids near the glass transition. (see their science paper if you can).

If we want to think about colloids as model atoms, which we do, then there's another property apart from just their size that we need to be able to control.

2. You can control their interactions

Being the size they are, if we didn't do anything to our colloids after making the spheres they would stick together quite strongly due to van de Waals forces - this is the attraction between any smooth surface to another, as used by clingfilm. To counteract this the clever experimentalists are able to graft a layer of polymers around onto the surface of the colloid.

It's like covering it with little hairs. When the hairs from two particles come into contact they repel, overcoming the van de Waals attraction. The particles are "stabilised". In this way it's possible to make colloids that interact pretty much like hard spheres. So not only can we use them as model atoms, but we can use them to test theoretical models as well!

Further to this the colloids can be charged and by adding salt to the solvent one can control the screening length for attraction or repulsion to other colloids. Finally there's the depletion interaction. I want to come back to this so for now I'll just say that by adding coiled up polymers into the soup we can create, and tightly control, attractions between the colloids. With this experimentalists can tune their particles to create a zoo of different behaviours.

3. They're thermal

If the colloids are not too small to be imaged, why not make them bigger? If we made them, say 1cm, then we could just sit and watch them, right? Well not really. If you filled a bucket with ball bearings and solution, density matched them so they don't sink or float and then waited, you'd be there a long time. The only way to move them in a realistic amount of time is to shake them - this is granular physics.

Granular physics is great but it's not what we're doing here. Real atoms are subject to random thermal motions and they seek to fit the Boltzmann distribution. For this to work with colloids they need to be sensitive to temperature.

When a colloid is immersed in a fluid it subject to a number of forces. If it's moving then there will be viscous forces, and on an atomistic level it is constantly being bombarded by the molecules that comprise the fluid. In the interests of keeping this post to a respectable size I can't go through the detail, but suffice it to say that this is an old problem in physics - Brownian motion.

Under Brownian motion the large particle will perform a random walk that is characterised by its diffusion constant. The bigger this number the quicker it moves around. A more intuitive number is the time it takes for a particle to move a distance of one particle diameter. When you solve the equation of motion for a large particle in a Stokesian fluid you find that this time is given by

where is viscosity, a is the particle diameter, and k_B T is Boltzmann's constant and temperature. Now this does get more complicated in dense systems and the properties of the fluid matter, but this is a good start. This could be a topic for another post.

For a typical colloidal particle, around a micron in size, you have to wait about a second for it to move its own diameter. For something only as big as a grain of sand you can be waiting hours or days. Even by 10 microns it's getting a bit too slow. But close to 1 micron, not only does it move about in an acceptable time frame, we can easily track it with our confocal microscope. If it's diffusing around then we can hope that it will be properly sampling the Boltzmann distribution - or at the very least be heading there. So once again, that micron size sweet spot is cropping up.

So what else?

Hopefully this serves as a good starting point to colloids. Obviously there's a lot more to it. An area that I'm very interested in at the moment is what happens when the colloids are not spheres but some other shape. I'll be posting more about it in the coming months.

If you don't remember anything else just remember that colloids are the perfect size to test statistical mechanics and to be visible.

So well done colloids, you're just right size.

Even colder still

In a previous post I was talking about how you can use a laser to cool atoms. By tuning the laser to just below the energy of an atomic transition you can selectively kick atoms that are moving towards the laser. If you fire six lasers in (one for each side of the cube) you can selectively kick any atom that is trying to leave the centre. So we've made a trap!

There is a hitch unfortunately. There is a minimum to which one can cool the atoms, once the atoms have an energy that is comparable to the photons coming from the laser then that's about as low as they can go. After all, there's only so much you can cool something by kicking it. We're already pretty cold - around 100 micro Kelvin - we'd like to go a bit colder if we can. Now we're into magnetic traps.

Magnetic Traps

Up to now we've been acting quite aggressively towards the atoms - kicking anything that's moving too quickly. To do better we're going try and round them up where we can control things better. Fortunately there's a neat way to do this. We can make use of an inhomogeneous magnetic field and the Zeeman effect.

If you apply a magnetic field to our gas of atoms then the magnetic dipoles of the atoms tend to line up with the field. Being quantum physics they can only do so in a discrete number of ways. What happens is that the transition that used to be a line splits and shifts into a number of different lines.

If we use a stronger field then the shift is larger. We can finely tune the energy at which our laser will interact with the atoms. So now we do this; if we put a magnetic field that is zero in the middle of the trap and gets bigger as you move away from the centre (you can do this) then we can control how hard we kick the atoms depending where they are. If we do it right then inside the trap we hardly kick them at all and outside trap we kick them back in.

Evaporation

We've managed to confine the atoms in our trap, the final step is to switch off the lasers (to stop all that noisy kicking and recoiling) and to try and use evaporation to get rid of as much energy as possible. It is understandably quite complicated to stop them all flying out once you've switched off the lasers and unfortunately it's at this point I start getting lost! The actual cooling mechanism is nothing more complicated than why your cup of tea goes cold.

After all this we're down the micro Kelvin level - a millionth of a degree above absolute zero! At these sort of temperatures the atoms can undergo a quantum phase transition and become a Bose-Einstein Condensate (BEC). This is a new state of matter, predicted by theory and finally observed in the nineties. As far as I know this is as cold as it gets anywhere in the universe.

Well I think I'm done with cooling things now. It starts off beautifully simple and then gets a bit harder! Needless to say I salute anyone that can actually do this - it's back to simulations for me.

EDIT: I over-link to wikipedia but this is a good page on Magneto-optical traps

Simulating a molecule with a quantum computer

Simulating a molecule

There's a fairly nifty paper out in PRL on simulating a molecule with a quantum computer. In principle doing calculations on quantum systems will be much faster with quantum computers (when they become a reality) thanks to being able to hold the computer in a superposition of states. These guys have had a bash using an NMR based "computer" - it's pretty fun.

Laser Cooling

Last semester I was helping out teaching a bit of quantum and atomic physics. It was quite fun going back to stuff I was a little hazy on the first time. I finally understand the periodic table for one thing. Another thing that I knew about but never really got the detail is laser cooling. This is really nice, I'll blast through it here. Watch out for the stat-mech bit, blink and you miss it.

In an atom electrons are not free to sit anywhere they want (more or less), they inhabit precisely defined quantum states that have well defined energies, angular momenta etc. Therefore if you give an atom a kick then it will release the energy you give it in precisely defined packets of energy. So if you take the light emitted by the atoms and put it through a spectrometer (could just be a prism) you'd see something like this, from here, for sodium.

You'll recognise the orange line from the street lamps that are slowly on their way out. I did a version of this experiment when I was an undergrad where we did the opposite, we shone white light through sodium gas and while most of it goes through the frequencies that match the right transition frequencies get absorbed and are missing from the final spectrum. Might look like this, ish

Notice that the lines aren't all that sharp whereas I said they should be precise lines. This is for a number of reasons. One is that the uncertainty principle doesn't like precise energies. There's an uncertainty attached to the lifetime of atomic transitions or collisions. Another, more important effect is Doppler shifting due to the temperature of the gas. We can assume that the atoms in the gas have a distribution of velocities that comes from the famous Boltzmann distribution

Light emitted from a moving atom will be Doppler shifted which will take our precise emission line and spread it out around the average. This property turns out to be very useful and what we'll use. First a mention about the laser.

Lasers are brilliant. With a laser you can send in a beam of photons with a highly tuned narrow band frequency. When a photon hits with a frequency that matches the absorption frequency of the atom, they collide and scatter. When it's too much or too little it will most likely just go straight through.

So finally we get to how you cool the gas. If you send in a laser pulse into a warm gas of atoms then different atoms will see different things. Thanks to the Doppler shift, an atom moving with speed, v, will see the laser frequency, f_0, Doppler shifted to (c = speed of light)

Atoms moving away from the laser see it red shifted (lower frequency), atoms moving toward the laser see it blue shifted (higher frequency). If we tune the laser to just below the absorption frequency of the atom then the only atoms that collide with the beam are those moving towards it (the ones that see the blue shift).

Were it not for the precision of the transition level the laser would equally kick atoms moving towards it and atoms moving away - adding no net energy into the system. However, if we only collide with atoms moving towards the beam then we can actually remove energy. What's even more staggering is that this actually works!

Laser cooling can make things seriously cold. You may have seen the headlines that the LHC is colder than space. Impressive given the size of the thing, but space is about 2 Kelvin. This is peanuts compared to laser cooling. This can get a gas down around 1 mK - that's a factor of a thousand. You can get even colder with new techniques but somehow laser cooling pleases me the most.

So that's laser cooling. It's beautifully simple, uses basic ideas from quantum mechanics, relativity, statistical mechanics and then makes something brilliant thanks to a laser.