Lecture – 3

Electron Pairing, Basics of BCS theory

 Let us, look at BCS theory. The Bardeen, Cooper, Schrieffer theory, the first microscopic
theory of superconductivity, which was extremely ,successful in describing, the behaviour
and the properties of the conventional superconductors, which are also known as weak
coupling superconductors.

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So, I said that it was the first microscopic theory and it was formulated by Bardeen, cooper
and Schrieffer and that's where the name BSC came, in 1957. Which was approximately 50
years, after the discovery of superconductivity experimentally, which as we have seen before,
that it was done by K modelling owns in 1908? This theory is successfully describes, the
superconducting properties, of weak coupling superconductors, will try to make it clear that,
what we coupling? The word weak coupling means, such as, aluminium and other materials,
mostly they are metals and not all metals from or give rise to superconductivity. But, there are
certain metals which give, this also will discuss, which the potential candidates for
superconductivity are. So, the basic idea is, that the electrons lying within Debye energy of a
filled Fermi sea. .Okay? So, those two electrons are needed and they are lying within the D
by a frequency or Debye energy of a filled Fermi sea in a metal, they can form bound pairs.
So, this is something that has to be contrasted from the usual behaviour of electrons, which
would repel each other, however, if you can create a situation in which they are in a very
close proximity of a filled Fermi sea, the electrons don't interact with the pharmacy, other
than by exclusion principle and then these two electrons, actually can have an attractive
interaction between them and can form bound pairs and it is important to say that ,not all
electrons participate in pairing and only the electrons, which are in the vicinity of the Fermi
surfaces do, not in the say the, near the ,centre of the Fermi surface ,they don't take part in
pairing. But, it's only which lie in the vicinity of the Fermi surface or close to the Fermi
energy they do, this paired state requires a many body description and this is what? Is the
central focus of our discussion, at least for, this one and a discussion, that's going to be held
after This now, this hint that the Debye energy scale is important for this problem, it actually
signals, that there is an involvement of electron-phonon interaction and this was proposed by
Frohlich , as early as 1950.

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So before this theory came up. Now, this electron- phonon interaction describes isotope
effect. Just give me a minute to say, what that is? So, the dependence on the sorry, this should
be phonon on, the phonon parameters were experimentally demonstrated by the fact, that the
transition temperature, we have seen this concept of transition temperature, a temperature that
divides superconducting state, with that of a non superconducting one or rather a metallic
state, the temperature at which this transition occurs is called as a superconducting transition
temperature. So this, transition temperature T C, becomes a function of the ionic mass, of our
different isotopes of the same metal. Now, that tells that if that happens then the lattice,
because the ions are involved and hence the lattice is involved and then the, the phonons are
involved as well and this is an experimental demonstration of an electron phonon interaction
or the rather the phonons are playing an important role in the whole process. So, if you want
to write this, this goes as a delta TC over TC, this is equal to a minus half Delta M over m,
where m is an ionic mass and Delta M is the difference in ionic masses of two isotopes or
very simply this is written as TC to be a function of you know, 1 by square root of M, where
m being the ionic mass. So, these are experimental demonstration, that the phonons are
involved and which is also central to the discussion that we are going to have,

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So, coming to the success of the BCS theory, a priori, of course we haven't talked about
BCS theory yet but, it's important to know that why should we be doing it in a course like this
there are many successes in fact it's, it gives the excitation energy gap, the energy gap so-
called in a superconductor there is certain amount of energy that is required to be supplied, to
the superconductor in order to break, the or rather the break the Cooper pairs and promote
them to the excited state so this is done experimentally are done by, the electron tunnelling
which was done by giver in 1960, so when an electron is sent across a metal in, metal
superconductor Junction the superconducting energy gap to Delta, it should not have been
able to pass through because there is a additional barrier that is, is there which the electron of
which the metallic side does not have but, however there is a process called as a Andreev,
reflection which we are not going to discuss here and because of that an three reflection there
is a pair, if not the electron there is a pair that can propagate into the superconducting region
and this shows up in a peak which is called as a Andreev peak and this happens just below
the energy, of the excitation energy of the of the gap of a superconductor and hence its it
gives these electron tunnelling measurements they idle the magnitude of the gap and there are
other experiments which actually probe, the symmetry of the gap, the symmetry of the gap in
the momentum space so, to say it explains Meissner effect, we have seen extensively what
Meissner effect is it explains the specific heat jump, it explains isotope effect as we have seen
and the important books in this context are, parks are deep ops he had two volumes of super
conductivity which were published in 1969 and then there's a Rickayzen, which there there's
a book by Rickayzen, which was in 1965 and then this book by, Schrieffer in 1964, one of the
proposals of BCS theory.
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So, what exactly is happening how, are the electrons interacting with themselves by, an
attractive interaction by, an attractive potential such that they form bound pairs and what do,
these bound pairs have in common with the superconducting state so, it can be understood as
the instability of the Fermi gas so what happens is that the ground state of the free Fermi gas
as we said that this corresponds to the filled Fermi sphere, corresponds to all completely
filled states up to the Fermi level and all states beyond, the Fermi energy they are all empty
this is the definition of the Fermi distribution function but, this Fermi gas is going to get
unstable against the formation of at least one bound pair irrespective of regardless of how,
weak the interaction is so long it's attractive and this was known as Cooper's instability so, to
rephrase this we have a field Fermi sea, or a Fermi sphere if by some means, what means we
are going to discuss just in a while if by some means that two electrons form bound pair in
the vicinity of that Fermi sphere, lying within the energy scale which is given by the phonon
frequency or, phonon energy then this Fermi gas, the free Fermi gas is going to be unstable
and this is called as the “Cooper's instability” to see how such attractive interactions come
about now, consider two electrons added to a filled Fermi sea, the electrons interact with each
other but, not with the Fermi sea except via the exclusion principle one sort of hand waving
way of seeing it is that suppose you have a horse, moving through a dusty field and when it
runs through the dusty field it gathers a lot of dust around it, and anybody say another horse,
would not see that horse but, would see a cloud of dust that is moving forward and pretty
much something similar to that is happening that an electron passes through the lattice and
because, of these the ions being present these pics of in a positive charge that it looks for
another, electron it looks like a positive charge and they form bound pairs, now it could also
be argued that why doesn't this other electron also is perceived, as a cloud of positive charge
which when they will repel and we'll see that this happens at different time scales and that's
why there is not enough time that both of them, would be like an ionic cloud moving together
and they would repel rather it happens at a shorter life time scale, that the, the electron, one
electron sees the other ionic cloud and gets attracted to it and forms a bound pair but, this is
just a hand waving way of seeing looking at it we will see this more carefully so, as has been
told that the first hunch, or the inkling, of the BCS theory what was put forward by

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Cooper in 1956, just a year ahead of the discovery of BCS theory .so, he pointed out, that a
normal metal, will become unstable, to the formation of pairs, if the I mean, no matter how
small the attractive interaction between the pair is and so he proposed that ,such pairing
would be preceded or would be facilitated by the presence of the lattice and hence phonons.
So, the electrons would scattered in a particular way and the electron-electron interaction, in
presence of phonons is given by, I will explain what all these quantities are? So, the first
term is the screened Coulomb potential and it's always positive and hence repulsive. So, in no
way, that this term can give rise to, an attractive interaction, the first term. Now, the second
term is generally, weaker than the first term and caused by electron phonon interaction, the
strength of which is given by, MQ. Now, this term can become negative, if Omega square is
less than, Omega D square. So, in general, this the frequencies lie around the Debye
frequency, as has been told earlier. So, in a small range, that e in the vicinity of Omega D, if
Omega becomes, less than Omega D, the energy denominator becomes small and negative.
So, the whole interaction term or this whole second term becomes, negative and large and this
can cause super conductivity. So, it will happen inner
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 Thus, I mean, vs. q Omega. Now, when the second term actually, takes over the first term.
The second term being negative, then the whole interaction, can become negative, in the
vicinity of the, of Omega D .Okay? so, it is possible that the two electrons, to bind, if they
construct a relative wave function ,which selectively uses a frequency range, that is given by
so, if you plot this, then it looks like that, it is so, this is a vs Q Omega and this is Omega and
it is in this range so it, it is in this range, that it's negative and one can have, an attractive
interaction .so ,once again to repeat it is that ,this is possible for the two electrons to bind , if
they can construct ,a wave function, which selectively chooses, the frequency ,the frequency
range, that is attractive, attractive, attractive. And in fact alkali metals, like sodium,
potassium, etcetera; alkali metals have very weak, electron phonon interaction and hence, do
not give rise to superconductivity .Okay? So now, so this interaction has to be in this regime
that is shown here

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And it is usually is as a competition of two terms, one term being necessarily positive and
repulsive, which is the screen Coulomb term, and the other term which arises because of the
electron phonon interaction, the strength of that being mq .but, because of a denominator,
which is a competition between, the energy of the pair versus, the energy of the ,the Debye
energy .so and then since Omega is close to Omega D, Omega is measured from the field for
me C , Omega is close to Omega D, if it can happen that Omega is less than Omega D, then
this term the denominator becomes small and negative and then we can have an attractive
interaction and that attractive interaction ,will actually give rise to super conductivity .but, we
haven't still derived or at least explain that, how this interaction term comes from ? And that
can be understood in two different ways, one is that rigorously taking an electron photon
matrix element or I draw the diagrams and calculate this term, the second term particularly.
There is another way, of doing that which is what we are going to do

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So, let's do the origin of .Okay? So, we have a scattering between case k, up and a minus K,
down electron .so, one could ask the question, that why is it? that one has one electron has a
momentum K, the other electron has a momentum minus K ,it can be shown that, with the
Momentum's being chosen in this particular fashion, a two particle state yields the minimum
energy, which is the most stable configuration and for a bound pair to happen ,because they're
in the same state, we cannot expect a both up ,up pair to occur or an up down, down pair to
occur. So, the pairing has to be between up and down, so these are the momentum and spin of
the participating electrons, which are participating in the bound pair. So, let's see that, how
these pairing takes place? Now, just to say that it's a spin independent interaction and so, spin
index can be dropped .Okay? So, let's say, the case one, the case one is that, that there is a
direct electron-electron interaction, which is facilitated by the Coulomb forces. So, let us ,
consider an initial state, so this case one is Coulomb interaction and it's a direct process, what
do I mean by direct process is? That, there is an initial state I, before scattering and there is a
final state F, after scattering. So, the matrix element of such a electron-electron interaction, in
such a direct process ,will just write e, e and dir, let's just give a bit of space here and this is
written as, is I He-e , dir and F and this can be written as exponential I, K dot R, which is a
plane wave initial state and you see, that's what we write as Coulomb and then exponential
minus I K prime dot R and D cube R ,so, this is the matrix element and this matrix elements,
K is the incoming state momentum, so the electron comes with a momentum K and leaves
with a momentum – I, mean leaves with a momentum K Prime, this minus sign is coming
because you are taking a kept here, whereas this is a bra here, so this is exponential I ,K
daughter. So, we have assumed that both I and F are plane wave states, I and F are plane
wave states. So, this term cannot give any negative contribution and hence it cannot account
for the two electrons to form a bound pair, so this is positive and hence it's repulsive. So, we
are not yet there, for getting the attractive interaction.

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 Now, let us look at, a case 2, which is an indirect process ,it takes place waier exchange of
phonons and this there is an intermediate process involved and it is that's, why it's a second
order process, remember your second order perturbation Theory ,where the way it is written
is that there is an intermediate ,there is an initial state and then there is a perturbation and
then there is a final state, I'm sorry, there's an intermediate state here and then this, another
matrix element and the final state and then here, one gets the energy , so I minus the
intermediate energy square. So, this is the correction, let's call it as e2, in the second order
perturbation theory. this is just a result that we are going to use, so there are two ways that
this indirect thing can take place, one is number one, in which the electron one, let's just label
them, even though they are indistinguishable this is for our convenience, so with momentum
key, emits a photon, which is later reabsorbed by electron 2 with momentum – K. let's just
say, this process once more. So, there is an electron, called electron one, which has a
momentum K, it emits a photon, which later, at a later time, the electron 2 absorbs this, which
had a momentum minus K and this process would be looked upon as this. So, this is the key,
which is electron number one and this is an electron minus K, this is electron 2, this one M
its ,k m its, photon of momentum Q .so, this becomes K plus Q and this becomes minus K,
minus Q and because two so ,this is time axis. So, this is how time increases and we are
particularly, you know talking about, that so this is the, this is how the time grows, so later
on, when after it emits it gets reabsorbed. Now, the same thing can be thought of for the
reverse case,

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that is 2 ,is that electron 2 , with momentum K, - k emits a photon, which is, is later
reabsorbed by electron ,electron one with momentum K .so, this is a similar thing, it's just
that the alignment of the figure will be a little different, so they'll be K here and it goes like
this and now because the process happens in the reverse order, so we'll draw it this way, so
this is electron one, with K, again it's K plus Q here and it is, minus K and this is minus K,
minus Q and we are talking about ,so this is the again the time, so these are the two
possibilities of the indirect process, that one emits the photon and the other absorbs it and
there's a time delay ,between that and in principle both can occur and both will have to be
considered. Now, you see that in both cases, the initial and final states are same.

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So, let us do this, that process one, process one, had initial is epsilon I, which is two Zi K,
which is epsilon K minus mum, so Zi K is equal to H cross square ,K square over 2m minus
mu and final is epsilon F which is two Zi K Prime and K prime equal to K plus Q. So, that's
the, that's for the process one and similarly for the process 2 , its initial is Zi equal to two Zi
K and F is equal to 2 Zi K prime, well I mean, this K is our vector. But, we are ignoring it at
the moment and so even if the initial and the final states are saying, I mean, the energies are
same. But, the inter amine, the initial and the final states are same. But, the intermediate
states are different and let's say, the intermediate step, so for process one, the intermediate is
equal to Zi k prime plus, Zi k plus, h cross Omega Q and for the second one, it's equal to Zi
K plus, Zi k prime plus, h cross Omega Q .so, energies are still same of the intermediate state.
Now, calculate the matrix elements, including these intermediate states.

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so, H e-e, in direct, using the same notation as earlier between ,I and F ,you have to sum over
the intermediate States and its I , H e-e in direct, I'll just write it, intermediate and
intermediate H e-e in direct, indirect means ,they exchange your phone on .so, they don't
directly interact and F and then there is a square of the matrix element. Now, it's either I or F
both of them being the same. and the square of that, so this is gives rise to an intermediate i,
H e-e indirect , intermediate and 1/2 of, 1/2 and 1 divided by E f minus e nth plus, 1 by E I
plus minus Eint and then we have, intermediate H e-e indirect and F and so on. So, these are
simply numbers. Because, these are matrix elements. So, this is summing over, over both 1
and 2 .so, this is written here, it's equal to 1 divided by Omega minus Omega Q, 1 divided by
Omega plus Omega Q. So, this becomes equal to 2 Omega Q, divided by Omega square
minus Omega Q Square and a VC, Q square, which is, so in, in essence, this exactly looks
like the second term, that we have gotten, with an energy denominator which is here, given
by this and if you want how this comes, then you can look at this thing, that e F minus e int,
inverse it's equal to ½ zi K prime, minus Zi K minus Zi K prime minus H cross Omega Q
and E I minus e int, inverse it's equal to 1/2 Zi K, minus Zi K prime, minus Zi K, minus H
prime Omega Q and also Zi K prime minus k, Zi has been used as H cross Omega Q .so,
this matrix elements are positive definite, this one, however because, of this energy
denominator and in that narrow that we have talked about, this could be attractive and hints
would give rise to the attractive interaction .

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Now, let us look at, the two particle wave function: BCA's gap equation .Okay? so, block
actually argued: lowest energy State for a two particle system, corresponds to zero total
momentum. So, the two electrons are equal and opposite momentum, two electrons which are
taking part in binding, so we can write down, the orbital wave function, it's only the orbital
part that we are writing it down ,two have, R 1 and R 2 equal to a gk exponential I K dot R 1,
exponential minus I K dot R 2, where GK is some weight or the amplitude of the wave
function. Now, when we write the full wave function, the orbital part would be symmetric or
anti-symmetric depending on the spin part beings anti-symmetric or symmetric because the
full wave function, consisting of the orbital part and the spin part will have to be anti-
symmetric. So, if we choose symmetric for this, then the spin part would be anti symmetric
and if we choose anti-symmetric part for this, then the spin part would be symmetric. But,
remember that we have done this earlier, for two spins, we can have four states, one of them
is called as a singlet state, which is an anti symmetry and the other three are called triplet
states, which are symmetric ,which means that if you interchange the particles then the wave
function does not change. So, because the spin part for a singlet wave function, is anti-
symmetric. So, the orbital part will choose will be chosen as symmetric. Now, this is also
shown, that it is generally true, for a two particle system, that the singlet one has a lower
energy .so, we take a singular choose a singlet wave function and BCS theory corresponds
to, singlet pairing. So, we have the singlet wave function as, up down - are down up: and this
is anti-symmetric and because this is anti-symmetric the orbital part has to be symmetric. So,
we take this, orbital part as and also we'll have to take, that K less than, I mean, K greater
than K. Because, we are writing down the two particle wave function ,which is residing just
outside the Fermi surface .so, it's GK and the cosine K dot R 1 minus R 2 and then up down -
r down. Now, this can be plugged, into the call this as equation 1.

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And this is plugged into the Schrodinger equation, so this is e minus 2 EK and a GK equal to
K prime greater than K F, so you used a vkk Prime and a G K Prime. So, all these are k's are
of course vectors. so ,VK k prime, are the matrix elements of the interaction potential and
vkk prime is something that we have seen, just a while back, but just to keep our discussion
simple, we'll take this as Coulomb term or rather, you can consider this VR to be arising from
that kind of a interaction ,which is mediated by phonons. So, R is the R is the distance
between two electrons, with momentum K and distance between two electrons and the VK k
prime of course 8, so VK k prime describes scattering of K prime, minus K prime, 2 K and
minus K .so, we are to solve for this is equation number to solve for G K ,such that, such that
total energy, E is less than two EF is basically that's the condition for a bound pair to exist . it
is very hard to do this calculation for a general potential. So, what you can do is that, a V KK
prime ,can be taken as a minus V, for epsilon F to be smaller than equal to epsilon KK prime
and smaller than equal to epsilon F plus H cross Omega D. So, this is as we have said earlier,
that it will be overall negative, because mediated by phonons, of course that has to be
satisfied, by the participating electrons, they have to choose the energy range, where it
becomes negative, but suppose it becomes negative and that the K and K prime for both the
electrons would have to lie between epsilon F to, epsilon F plus h cross Omega T, it's equal to
zero, otherwise.

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Now, with this, we have GK, if you put it there, it becomes equal to a K Prime and G K
Prime and two epsilon K minus e. Now, sum over K, so it becomes one over V, this V is the
strength of the interaction and we just reiterate that, this V could be infinitesimally small, a
super conductivity will still occur. So, this is equal to sum over K and greater than KF,1 by 2
epsilon K minus e. Now. We can replace the summation by integration and we had to just
invoke the density of states. But as we have told several times .that the super conductivity is a
phenomenon that happens very near to the Fermi surface. So, while we convert the sum into
an integral, we don't need to take, the energy dependence of the density of states, rather we
can take the density of states at the Fermi level. So, this is equal to n epsilon F and the
integration has to be done, not over all energies. but ,what is the relevant scale is this and then
it is 2 epsilon minus e, this epsilon is a running variable, this capital epsilon is the two
particle energy, its n EF once we do the integration ,it becomes log of 2 epsilon F minus
epsilon plus h cross Omega D and we have 2 epsilon f minus e .so, that's the equation that
one gets and now, for conventional superconductors, n epsilon F into V ,is usually of the
order of 0.3 or less than 0.3. So, this is what is meant by the weak coupling approximation
which demands, that n epsilon F, V has to be less than 1 or, or maybe much lesser than 1. So,
this is weak coupling superconductors.

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So then, we have 2 divided by n e F into V ,equal to log of 2 epsilon F - e + 2 H cross Omega
D ,divided by 2 epsilon F minus E and now, if I want to free this log, we have a to epsilon F -
e + 2 H cross Omega D ,divided by 2 epsilon F minus E and this has to be exponential 2
divided by n EF into V and if you solve for e ,it becomes equal to so I can, I can multiply this
here and just doing one more step, I would land up with this 2 H cross Omega D exponential
minus 2 by n EF into V. So, this is the energy of, total energy of the two particle system and
so, this is with respect to , if we take it with respect to the Fermi surface of the two electrons,
this is comes with a negative sign and this negative sign ,talks about that, they have a bound
,they are bound , they are in bound state .so, a bound state can form off infinitesimally, this is
not committed to the magnitude of V, any magnitude of V would do. So, by an infinitesimal
attractive interaction, also you see, that the binding energy is non analytic, it comes as an
exponential and hence no orders of perturbation theory, can bring this, this result. our
perturbation theory in orders or in terms of V, the strength of the attractive interaction
between the electrons, just one more thing that we need to do here, is that so, for the wave
function,

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we have, the amplitude of the wave function which is GK, this is equal to a cosine K dot R,
divided by 2 Zi k plus e prime, where as Zi k equal to epsilon K minus mu and which is equal
to epsilon K minus epsilon F at T equal to 0 and E prime equal to 2 epsilon F minus E ,which
is of course, greater than 0. So, e Prime can now be called as, binding energy .and this K has
to be greater than KF, just a few comments, this weighting factor ,which is given by 1 divided
by Zi K Plus, has a maximum at, at one over e prime for Zi k equal to zero. which are valid
or which are applicable for electrons at the Fermi surface and it falls off at positive values of
zi K. so, if you note that ,the e prime The Binding energy is much smaller than ,the H cross
Omega D ,for n epsilon F to be into v to be less than one. so this makes sure that the detailed
behaviour of V KK prime is not important, also the small energy range, allows the estimation
of the range of the Cooper pairs ,which we know is called as the coherence length and that
coherence length, is given by ,this is what has been told earlier and this is of the order of 1 in
BCS theory it's sort of the order of 0.8 and that gives a good estimation of the coherence
length of the Cooper pair, wave function and that matches with the experimental values
which are of the order of maybe 3 to 5000 angstrom. So, this is a theory ,which gave, the
calculation had given rise to a gap ,the main features of the gap is that, it is valid for any
strength of the electron-electron interaction, so long is attractive, it is a non perturbative, the
result is non perturbative and hence you cannot do a perturbation theory of any order in order
to get this result and also it allows the estimation of the, the extent of the Cooper pair wave
function, which is called as the coherence length.