# Tag Archives: Cooper pairing

## Landau Theory and the Ginzburg Criterion

The Landau theory of second order phase transitions has probably been one of the most influential theories in all of condensed matter. It classifies phases by defining an order parameter — something that shows up only below the transition temperature, such as the magnetization in a paramagnetic to ferromagnetic phase transition. Landau theory has framed the way physicists think about equilibrium phases of matter, i.e. in terms of broken symmetries. Much current research is focused on transitions to phases of matter that possess a topological index, and a major research question is how to think about these phases which exist outside the Landau paradigm.

Despite its far-reaching influence, Landau theory actually doesn’t work quantitatively in most cases near a continuous phase transition. By this, I mean that it fails to predict the correct critical exponents. This is because Landau theory implicitly assumes that all the particles interact in some kind of average way and does not adequately take into account the fluctuations near a phase transition. Quite amazingly, Landau theory itself predicts that it is going to fail near a phase transition in many situations!

Let me give an example of its failure before discussing how it predicts its own demise. Landau theory predicts that the specific heat should exhibit a discontinuity like so at a phase transition:

However, if one examines the specific heat anomaly in liquid helium-4, for example, it looks more like a divergence as seen below:

So it clearly doesn’t predict the right critical exponent in that case. The Ginzburg criterion tells us how close to the transition temperature Landau theory will fail. The Ginzburg argument essentially goes like so: since Landau theory neglects fluctuations, we can see how accurate Landau theory is going to be by calculating the ratio of the fluctuations to the order parameter:

$E_R = |G(R)|/\eta^2$

where $E_R$ is the error in Landau theory, $|G(R)|$ quantifies the fluctuations and $\eta$ is the order parameter. Basically, if the error is small, i.e. $E_R << 1$, then Landau theory will work. However, if it approaches $\sim 1$, Landau theory begins to fail. One can actually calculate both the order parameter and the fluctuation region (quantified by the two-point correlation function) within Landau theory itself and therefore use Landau theory to calculate whether or not it will fail.

If one does carry out the calculation, one gets that Landau theory will work when:

$t^{(4-d)/2} >> k_B/\Delta C \xi(1)^d \equiv t_{L}^{(4-d)/2}$

where $t$ is the reduced temperature, $d$ is the dimension, $\xi(1)$ is the dimensionless mean-field correlation length at $T = 2T_C$ (extrapolated from Landau theory) and $\Delta C/k_B$ is the change in specific heat in units of $k_B$, which is usually one per degree of freedom. In words, the formula essentially counts the number of degrees of freedom in a volume defined by  $\xi(1)^d$. If the number of degrees of freedom is large, then Landau theory, which averages the interactions from many particles, works well.

So that was a little bit of a mouthful, but the important thing is that these quantities can be estimated quite well for many phases of matter. For instance, in liquid helium-4, the particle interactions are very short-ranged because the helium atom is closed-shell (this is what enables helium to remain a liquid all the way down to zero temperatures at ambient conditions in the first place). Therefore, we can assume that $\xi(1) \sim 1\textrm{\AA}$, and hence $t_L \sim 1$ and deviations from Landau theory can be easily observed in experiment close to the transition temperature.

Despite the qualitative similarities between superfluid helium-4 and superconductivity, a topic I have addressed in the past, Landau theory works much better for superconductors. We can also use the Ginzburg criterion in this case to calculate how close to the transition temperature one has to be in order to observe deviations from Landau theory. In fact, the question as to why Ginzburg-Landau theory works so well for BCS superconductors is what awakened me to these issues in the first place. Anyway, we assume that $\xi(1)$ is on the order of the Cooper pair size, which for BCS superconductors is on the order of $1000 \textrm{\AA}$. There are about $10^8$ particles in this volume and correspondingly, $t_L \sim 10^{-16}$ and Landau theory fails so close to the transition temperature that this region is inaccessible to experiment. Landau theory is therefore considered to work well in this case.

For high-Tc superconductors, the Cooper pair size is of order $10\textrm{\AA}$ and therefore deviations from Landau theory can be observed in experiment. The last thing to note about these formulas and approximations is that two parameters determine whether Landau theory works in practice: the number of dimensions and the range of interactions.

*Much of this post has been unabashedly pilfered from N. Goldenfeld’s book Lectures on Phase Transitions and the Renormalization Group, which I heartily recommend for further discussion of these topics.

## Why Was BCS So Important?

BCS theory, which provides a microscopic framework to understand superconductivity, made us realize that a phenomenon similar to Bose-Einstein condensation was possible for fermions. This is far from a trivial statement, though we sometimes think of it as so in present times.

A cartoon-y scheme to understand it is in the following way. We know that if you put a few fermions together, you can get a boson, such as 4-helium. It was also known well before BCS theory, that one gets a phenomenon reminiscent of Bose-Einstein condensation, known as superfluidity, in 4-helium below 2.17K. The view of 4-helium as a Bose-Einstein condensate (BEC) was advocated strongly by Fritz London, who was perhaps the first to think of it in such a way.

Now let us think of another type of boson, a diatomic molecule, as seen in gas form below:

Even if the individual atoms were fermions, one would then predict that if this bosonic diatomic gas molecule could remain in the gas phase all the way down to low temperature, that at some point, this diatomic gas would condense into a BEC. This idea is correct and this is indeed what is observed.

However, the idea of a BEC becomes a little more cloudy when one considers a less dilute diatomic gas where the atoms are not so strongly bound together. In that case, the cartoon starts to look something like this:
Here the “diatomic molecules” are overlapping, and it is not easy to see which atoms are paired together to form the diatomic molecule, if one can even ascribe this trait to them. In this case, it is no longer simple to see whether or not BEC will occur and indeed if there is a limit in distance between the molecules that will necessarily give rise to BEC.

This is the question that BCS theory so profoundly addresses. It says that the “diatomic molecules” or Cooper pairs can span a great distance. In superconducting aluminum, this distance is ~16,000 Angstroms, which means the Cooper pairs are wildly overlapping. In fact, in this limit, the Cooper pair is no longer strictly even a boson, in the sense that Cooper pair creation and annihilation operators do not obey Bose-Einstein commutation relations.

However, the Cooper pair can still qualitatively thought of as a pseudo-boson that undergoes pseud0-BEC, and this picture is indeed  very useful. It enabled the prediction of pseud0-BEC in neutron stars, liquid 3-helium and ultra-cold fermionic gases — predictions which now have firm experimental backing.

An interesting note is that one can study this BCS-to-BEC crossover in ultracold Fermi gases and go from the overlapping to non-overlapping limit by tuning the interaction between atoms and I’ll try to write a post about this in the near future.

So while BCS theory has many attributes that make it important, to my mind, the most profound thing is that it presents a mechanism by which weakly interacting fermionic pairs can condense into a pseudo-BEC. This is not at all obvious, but indeed what happens in nature.

Update: In light of the description above, it seems surprising that the temperature at which Cooper pairs form is the same temperature at which they seem to condense into a pseudo-BEC. Why this is the case is not obvious and I think is an open question, especially with regards to the cuprates and in particular the pseudogap.

## Macroscopic Wavefunctions, Off-Diagonal Long Range Order and U(1) Symmetry Breaking

Steven Weinberg wrote a piece a while ago entitled Superconductivity for Particular Theorists (pdf!). Although I have to admit that I have not followed the entire mathematical treatment in this document, I much appreciate the conceptual approach he takes in asking the following question:

How can one possibly use such approximations (BCS theory and Ginzburg-Landau theory) to derive predictions about superconducting phenomena that are essentially of unlimited accuracy?

He answers the question by stating that the general features of superconductivity can be explained using the fact that there is a spontaneous breakdown of electromagnetic gauge invariance. The general features he demonstrates are due to broken gauge invariance are the following:

1. The Meissner Effect
2. Flux Quantization
3. Infinite Conductivity
4. The AC Josephson Effect
5. Vortex Lines

Although not related to this post per se, he also makes the following (somewhat controversial) comment that I have to admit I am quoting a little out of context:

“…superconductivity is not macroscopic quantum mechanics; it is the classical field theory of  a Nambu-Goldstone field”

Now, while it may be true that one can derive the phenomena in the list above using the formalism outlined by Weinberg, I do think that there are other ways to obtain similar results that may be just as general. One way to do this is to assume the existence of a macroscopic wave function. This method is outlined in this (illuminatingly simple) set of lecture notes by M. Beasley (pdf!).

Another general formalism is outlined by C.N. Yang in this RMP, where he defines the concept of off-diagonal long range order for a tw0-particle density matrix. ODLRO can be defined for a single-particle density matrix in the following way:

$\lim_{|r-r'| \to \infty} \rho(r,r') \neq 0$

This can be easily extended to the case of a two-particle density matrix appropriate for Cooper pairing (see Yang).

Lastly, there is a formalism similar to that of Yang’s as outlined by Leggett in his book Quantum Liquids, which was first developed by Penrose and Onsager. They conclude that many properties of Bose-Einstein Condensation can be obtained from again examining the diagonalized density matrix:

$\rho(\textbf{r},\textbf{r}';t) = \sum_i n_i(t)\chi_i^*(\textbf{r},t)\chi_i(\textbf{r}',t)$

Leggett then goes onto say

“If there is exactly one eigenvalue of order N, with the rest all of order unity, then we say the system exhibits simple BEC.”

Again, this can easily be extended to the case of a two-particle density matrix when considering Cooper pairing.

The 5-point list of properties of superconductors itemized above can then be subsequently derived using any of these general frameworks:

1. Broken Electromagnetic Gauge Invariance
2. Macroscopic Wavefunction
3. Off-Diagonal Long Range Order in the Two-Particle Density Matrix
4. Macroscopically Large Eigenvalue of Two-Particle Density Matrix

These are all model-independent formulations able to describe general properties associated with superconductivity. Items 3 and 4, and to some extent 2, overlap in their concepts. However, 1 seems quite different to me. It seems to me that 2, 3 & 4 more easily relate the concepts of Bose-Einstein condensation to BCS -type condensation, and I appreciate this element of generality. However, I am not sure at this point which is a more general formulation and which is the most useful. I do have a preference, however, for items 2 and 4 because they are the easiest for me to grasp intuitively.

Please feel free to comment, as this post was intended to raise a question rather than to answer it (which I cannot do at present!). I will continue to think about this question and will hopefully make a more thoughtful post with a concrete answer in the future.

## A Critical Ingredient for Cooper Pairing in Superconductors within the BCS Picture

I’m sure that readers that are experts in superconductivity are aware of this fact already, but there is a point that I feel is not stressed enough by textbooks on superconductivity. This is the issue of reduced dimensionality in BCS theory. In a previous post, I’ve shown the usefulness of the thinking about the Cooper problem instead of the full-blown BCS solution, so I’ll take this approach here as well. In the Cooper problem, one assumes a 3-dimensional spherical Fermi surface like so:

3D Fermi Surface

What subtly happens when one solves the Cooper problem, however, is the reduction from three dimensions to two dimensions. Because only the electrons near the Fermi surface condense, one is really working in a shell around the Fermi surface like so, where the black portion does not participate in the formation of Cooper pairs:

Effective 2D Topology Associated with the Cooper Problem

Therefore, when solving the Cooper problem, one goes from working in a 3D solid sphere (the entire Fermi sea), to working on the surface of the sphere, effectively a 2D manifold. Because one is now confined to just the surface, it enables one of the most crucial steps in the Cooper problem: assuming that the density of states ($N(E)$) at the Fermi energy is a constant so that one can pull it out of the integral (see, for example, equation 9 in this set of lecture notes by P. Hirschfeld).

The more important role of dimensionality, though, is in the bound state solution. If one solves the Schrodinger equation for the delta-function potential (i.e. $V(x,y)= -\alpha\delta(x)\delta(y)$) in 2D one sees a quite stunning (but expected) resemblance to the Cooper problem. It tuns out that the solution to obtain a bound state takes the following form:

$E \sim \exp{(-\textrm{const.}/\alpha)}$.

Note that this is exactly the same function that appears in the solution to the Cooper problem, and this is of course not a coincidence. This function is not expandable in terms of a Taylor series, as is so often stressed when solving the Cooper problem and is therefore not amenable to perturbation methods. Note, also, that there is a bound state solution to this problem whenever $\alpha$ is finite, again similar to the case of the Cooper problem. That there exists a bound state solution for any $\alpha >0$ no matter how small, is only true in dimensions two or less. This is why reduced dimensionality is so critical to the Cooper problem.

Furthermore, it is well-known to solid-state physicists that for a Fermi gas/liquid, in 3D $N(E) \sim \sqrt{E}$, in 2D $N(E) \sim$const., while in 1D $N(E) \sim 1/\sqrt{E}$. Hence, if one is confined to two-dimensions in the Cooper problem, one is able to treat the density of states as a constant, and pull this term out of the integral (see equation 9 here again) even if the states are not confined to the Fermi energy.

This of course raises the question of what happens in an actual 2D or quasi-2D solid. Naively, it seems like in 2D, a solid should be more susceptible to the formation of Cooper pairs including all the electrons in the Fermi sea, as opposed to the ones constrained to be close to the Fermi surface.

If any readers have any more insight to share with respect to the role of dimensionality in superconductivity, please feel free to comment below.

## Draw me a picture of a Cooper pair

Note: This is a post by Brian Skinner as part of a blog exchange. He has his own blog, which I heartily recommend, called Gravity and Levity. He is currently a postdoctoral scholar at MIT in theoretical condensed matter physics.

The central, and most surprising, idea in the conventional theory of superconductivity is the notion of Cooper pairing. In a Cooper pair, two electrons with opposite momentum somehow manage to overcome their ostensibly enormous repulsive energy and bind together to make a composite bosonic particle. These composite bosons are then able to carry electric current without dissipation.

But what does a Cooper pair really look like? In this post I’m going to try to draw a picture of one, and in the process I hope to discuss a little bit of physical intuition behind how Cooper pairing is possible.

To begin with, one should acknowledge that the “electrons” that comprise Cooper pairs are not really electrons as God made them. These electrons are the quasiparticles of Fermi liquid theory, which means that they are singly-charged, half-spinned objects that are dressed in excitations of the Fermi sea around them. In particular, each “electron” that propagates through a metal carries with it a screening atmosphere made up of local perturbations in charge density. Something like this:

That distance $r_s$ in this picture is the Thomas-Fermi screening radius, which in metals is on the same order as the Fermi wavelength (generally $\sim 5 - 10$ Angstroms). At distances much longer than $r_s$, the electron-electron interaction is screened out exponentially.

What this screening implies is that as long as the typical distance between electrons inside a Cooper pair is much longer than the Fermi wavelength (which it has to be, since there is really no concept of an electron that is smaller than the Fermi wavelength), the mutual Coulomb repulsion between electrons isn’t a problem. Electrons that are much further apart than $r_s$ simply don’t have any significant Coulomb interaction.

But, of course, this doesn’t explain what actually makes the electron stick together.  In the conventional theory, the “glue” between electrons is provided by the electron-phonon interaction. We typically say that electrons within a Cooper pair “exchange phonons”, and that this exchange mediates an attractive interaction. If you push a physicist to tell you what this exchange looks like in real space, you might get something like what is written in the Wikipedia article:

An electron moving through a conductor will attract nearby positive charges in the lattice. This deformation of the lattice causes another electron, with opposite spin, to move into the region of higher positive charge density. The two electrons then become correlated.

This kind of explanation might be accompanied by a picture like this one or even an animation like this one, which attempt to schematically depict how one electron distorts the lattice and creates a positively-charged well that another electron can fall into.

But I never liked these kind of pictures. Their big flaw, to my mind, is that in metals the electrons move much too fast for it to make sense. In particular, the Fermi velocity in metals is usually on the order of $10^6$ m/s, while the phonon velocity is a paltry $(\text{few}) \times 10^3$ m/s. So the idea that one electron can create a little potential well for another to fall into simply doesn’t make sense dynamically. By the time the potential well was created by the slow rearrangement of ions, the first electron would be long gone, and it’s hard to see any meaningful way in which the two electrons would be “paired”.

The other problem with the picture above is that it doesn’t explain why only electrons with opposite momentum can form Cooper pairs. If Cooper pairing came simply from one electron leaving behind a lattice distortion for another to couple to, then why should the pairing only work for opposite-momentum electrons?

So let me advance a different picture of a Cooper pair.

It starts by reminding you that the wavefunction for a (say) right-going electron state looks like this:

$\psi_R \sim e^{i (k x - \omega t)}$.

The probability density for the electron’s position in this state, $|\psi_R(x)|^2$, is uniform in space.

On the other hand, the wavefunction for a left-going electron state looks like

$\psi_L \sim e^{i (-k x - \omega t)}$.

It also has a uniform probability distribution. But if you use the two states (one with momentum $+k$ and the other with momentum $-k$) to make a superposition, you can get a state $\psi_C = (\psi_R + \psi_L)/\sqrt{2}$ whose probability distribution looks like a standing wave: $|\psi_C|^2 \sim \cos^2(k x)$.

In other words, by combining electron states with $+k$ and $-k$, you can arrive at an electron state where the electron probability distribution (and therefore the electron charge density) has a static spatial pattern.

Once there is a static pattern, the positively charged ions in the crystal lattice can distort their spacing to bring themselves closer to the regions of large electron charge density. Like this:

In this way the system lowers its total Coulomb energy.  In essence, the binding of opposite-momentum electrons is a clever way of effectively bringing the fast-moving electrons to a stop, so that the slow-moving ionic lattice can accommodate itself to it.

Of course, the final piece of the picture is that the Cooper pair should have a finite size in space – the standing wave can’t actually extend on forever. This finite size is generally what we call the coherence length $\xi$. Forcing the two electrons within the Cooper pair to be confined within the coherence length costs some quantum confinement energy (i.e., an increase in the electron momentum due to the uncertainty principle), and this energy cost goes like $\sim \hbar v/\xi$, where $v$ is the Fermi momentum. So generally speaking the length $\xi$ should be large enough that $\hbar v / \xi \lesssim \Delta$ where $\Delta$ is the binding energy gained from Cooper pairing.  Usually these two energy scales are on the same order, so that $\xi \sim \hbar v / \Delta$.

Putting it all together, my favorite picture of a Cooper pair looks something like this:

I’m certainly no expert in superconductivity, but this picture makes much more sense to me than the one in Wikipedia.

Your criticisms or refinements of it are certainly welcome.

Author’s note: Thanks to Mike Norman, who taught me this picture over lunch one day.