Unified Theory of Superconducting and

Superinsulating in Atomic-Scale

Liang-you Zheng*
Department of Chemistry
Center for Molecular Dynamics and Energy transfer
The Catholic University of America
Washington D.C. 20064

Abstracts: In this paper we dedicate to create a theory which not only can
explain the occurrences of superconducting phenomena but also can explain
the occurences of superinsulating phenomena in the same object materials, in
some conditions.

Keywords: of superconducting, superinsulating, Cooper pair, Unified Theory

1. Introduction.

Recently, researchers have discovered the insulating phenomena, in which cooper

pair has be found.1), 2) Cooper pair can be found in the superconducting materials
and in the superinsulating materials either. Cooper pair can guide the charges flow
and can block the current flow. In this paper, we use the two-site small bipolaron
model and in the one-dimension framework to explain this physics phenomena.
We need a theory not only to explain the superconductivity to occur but also to
explain the superinsulating phenomena to appear in the same materials. This
paper is exactly for this purpose.

2. Theory
We take the TiN’s (100) plane 3), current flows from left to right. Therefore, we
use the Ti-----N----Ti------N---as one dimension chain model.

• → −− ← o − − − −• → −− ← o − − − −• → −− ← o − − − − • → − − ← − o

• − − − − −o → − ← • − − − − − o → − ← • − − − −o → − ← • − − − − − o

Ti N Ti N Ti N Ti N

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 Fig. 1 Vibration between Ti and N atoms

ˆ and atom vibration Hˆ

In general, the Hamiltonian of the electronic H
e a
and the
Hamiltonian of the system may be written as

Hˆ = Hˆ + Hˆ (1)
e a

where
 2 
pi
H e = ∑i hi = ∑i  2m + ∑n V (r i − Rn )
 (2)
 
and
K
( un +1−un) + M2
2

H$ =∑
n 2
a
n 2 u& n
(3)

In the tight-binding approximation, the electronic Hamiltonian reads as

Hˆ e
= −∑ t (Rn +1 − R n ) C n +1 C n + C n C n +1 ( + +
) (4)
n

where t (Rn +1 − R n ) is the interaction of two nearest neighbor ions with the
electron. R n +1 and R n
are the instantaneous position of the (n+1)th ion
and the nth ion. Because the displacement of the nth ion u n
and u n +1 around
the instantaneous position R n and R n +1 are very small, the difference
between the distance of neighboring ions can reads as:

− Rn + (u n +1 − u n )
(0 ) (0 )
R n +1
− Rn = R n +1

(0 ) (0 )
and the distance of equilibrium position R n +1
− Rn = a the lattice constant
is very small.In that case, u n +1
− u n << a . Therefore,the interaction can be
expanded as
t (R n +1 )
− Rn = t 0 − γ (u n +1
− un ) (5)
( (0 )
where t 0 = t R n +1 − R n
(0 )
)
is the interaction between the electron
and the nearest-neighbor ions in their equilibrium position and the
dt
γ =− is the rate of the change of the interaction with respect to the
dx
distance between ions within a unit cell.

Substituting Eq.(5) into Eq.(4) and taking into account the spin of the

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Electrons, we have

Hˆ e
[ ](
= −∑ t 0 − γ (u n+1 − u n ) C n +1, s C n , s + C n C n +1, s
+ +
) (6)
n,s

The total Hamiltonian is now written as the sum of Eq.( 3 ) and Eq.(6)

Hˆ = Hˆ + Hˆe a
[ ](
= −∑ t 0 − γ (u n +1 − u n ) C n +1, s C n , s + C n, s C n+1, s
+ +
)
n,s

+ ∑
K
n  2
(u n +1−u n) + M2 2
n 2
u& 
n


(7)

We can prove that Eq.(6) is equivalent to Eq.(2) in the tight-binding approximation Su

et al. 4),5) first applied Eq.(7) to the trans-Polyacetylene. They considered Eq.(5) as the
standard form of the electron-phonon coupling in metals .

3. Canonical Transformation8)

As we have taken the model as a two-site small bipolaron mechanism. One spin is
up and the other spin must be down. Total spin of system must be zero. This is the
spin singlet of system. In that case, we can eliminate the label “s” in Eq.(7). And
then, we can change the Eq.(7) as follows

Hˆ [ ](
= −∑ t 0 − γ (u n+1 − u n ) C n +1 C n + C n C n +1
+ +
)
n

+ ∑ h ω q  aq a q + 
+ 1
(8)
q  2

According to the dynamical theory of crystal lattice 6), 7), we have

u =∑ n
q
h
2 NM ω q
(a + a )exp(i2πqna )
q
+
q
(9)

ω
+
where a q
and a q are phonon operation ,and q
is the frequency of the phonon.

Evaluating the spectrum of electron is equivalent to diagonizing the Hamiltonian

+
operator. For this, we transform of operator C n
and C n from the Bloch representation
to the Wannier representation :

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 ∑ exp(i 2πk n a )(C + C )
1
=
e o
Cn 0 N k
0 k k

∑ exp(i 2π n a )(C − C )
1
=
e o
Cn e N k
e k k
( 10 )

where Cn o
is the operator of an electron on the site of odd-numbered ion.

Cn e
is theoperator of an electron on the site of even-numbered ion.
For the part of the electron Hamiltonian
Hˆ e
= −∑ [t o
](
− γ (u n+1 − u n ) C n +1 C n + C n C n +1
+ +
) (11)
n
Through the transformation, we can get

 (k )( e + e + 0+ 0 ) 
 E0 C k Ck C k C k 
Hˆ e = ∑k − ∑ Bk ,q aq + a+q C ek+ C ek + C 0k + C 0k 
 q 
( )( ) (12)

where E (k ) = −2 t
0 0
cos(2πka ) (13)
and

B = 2γ cos(2πka )
h
[i 2πqa] (14)
k ,q
2 NM ω q

under the limit of the long wave length.

If we assume that the probability of an electron create or annihilation, respectively,

around odd-numbered ions is equivalent to the probability of creation and annihilation of
an electron around even-numbered ions (for two-site small bipolaron, that is true) i.e.

e+ 0+
C C =C C
e 0
k k k k

and

e+ 0+ +
C C +C C = n + n = n =
e 0 e 0 B
k k k k k k k BB k k
(15)

Therefore, we have

Hˆ e
= Hˆ eB
=∑
k
[E (k ) − Hˆ ]B B
0 k
+
k k
. (16)

Here,

* E-mail: Zheng@CUA.Edu 4
 Hˆ k
(
= ∑ B k ,q a q + a q
+
) (17)
q

The total Hamiltonian of the system is now rewritten as

Hˆ = Hˆ e, B
ˆ =∑
+H
a
k
[E (k ) − Hˆ ]B B + ∑ hω  a a + 12 
0 k
+
k k
q
q
+
q q
(18)

Now let us making a canonical transformation

Hˆ = exp(− s ) H
ˆ exp(s ) (19)
T

where

s = ∑∑
B
hω q
k ,q
(a + a )B B
q
+
−q
+
k k
(20)
k q

Therefore, we obtain

Hˆ =∑ [E (k ) − ∆ ]B B + ∑ h ω  a a
0 k
+
k k
+ 1
+  (21)
 2
T q q q
k q
2

Bk,q
where ∆ k
=∑
q hω q
(22)

The quantity ∆ k for the two-site small bipolaron is the binding energy of two
polarons. And call it as superconducting energy gap either.

4. Calculation of Superconducting critical temperature Tc 10)

Let
E (k ) − ∆ , E = hω q , n
+
E k
= 0 k q ˆ q = aq aq (23)

Therefore, from Eq.(21) we have

 1
Hˆ = ∑ Ek n
ˆ + ∑ E q n
ˆ +  (24)
 2
T k q
k q

We will make a calculation of Tc starting from Eq. (24). The strategy

is that we regard superconducting system as a system consisting of boson
particle gas. They obey the boson statistical law within grand canonical
ensemble. Firstly, we calculate the grand partition function Zg according to
the definition of grand partition function

Z g
[ (
= Tr exp − β Hˆ − µNˆ )] (25)

* E-mail: Zheng@CUA.Edu 5
where

Ĥ the Hamiltonian of boson particle gas

N̂ the operator of total number of particle of system

µ the chemical potential

1
β=
k B
T

Secondly, we calculate the thermodynamics potential Ω

Ω = − k B T ln Z g ( ) (26)

And then according to the definition we can calculate the total number of
particle

∂Ω
N =− (27)
∂µ

and the Helmholtz free energy

F = Ω + µN (28)

Using the stability condition of superconducting system

∂F
∂ ∆k ∆ k
∂F = δ =0 (29)

We obtain the equation of satisfaction of relationship between superconducting

energy gap and temperature. From this, we can calculate the Tc.

In the occupation representation, the state vector of boson particle system is

{n } = {n }, {n } = {n } {n }
k q k q

= n n k1 k2
...... nki ....... nq1 n q2
...... nqi .......... (30)

According to the definition of grand partition function9)

Z g
[ (
= Tr exp − β Hˆ − µNˆ )]

* E-mail: Zheng@CUA.Edu 6
i.e.

Z g
= ∑ {n} exp − β Hˆ − µNˆ [ ( )] {n}
{n}

 
= ∑ {n} exp − β  ∑ E k n
ˆ k

+ ∑ E q n

ˆ q
1
+ −µ
2
(nˆ + nˆ ) {n}
k q
{n}   k q 

∑ {n } exp− β ∑ (E − µ )N k {n } *
 
{ }
k k k
nk k 
=
∑ {n } exp− β ∑  E {n }
  1 
+  N q
{ }
nq
q
 q
q
2 
q

∑n k1
[
exp − β (E k 1 − µ ) ] n ∑ ......∑ ....................
k1
nk 1 nk 2 n ki
=
  1 
∑n exp − β  E q1 +  nq1 ∑ ........∑ ...............
  2 
q1
nq1 n q1 nqi

1 1
=∏
k [
1 − exp − β (ε k − ∆ k )] ∏ 1 − exp(− β
q E)
q
(31)

where ε k
= E (k ) − µ
0

From ( 26 ), ( 27 ), (28) and ( 31 ) we obtain

µβ exp[− β (ε k − ∆ k )] = exp[− β (ε k − ∆k )] − 1 (32)

This is the equation of relationship between superconducting

energy gap and temperature.

When T = Tc we request ∆ k
= 0 . In this case, we have

{
µ β c exp − β c ε k = exp − β c ε k − 1
c
} { c
} (33)

This is the transcendental equation. Here

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 β E (k ) − µ
1
= ε =
c
k 0
c
kT B c

Tc is critical temperature of superconductivity, kB is Boltzmann constant. Solving

equation (33) we obtain

µ
T c
= (34)
k B

After considering the modification with temperature, from Equation (34) we have

k T = 3.31 h n
2
3 (35)
B c **
m
**
where m is the mass of bipolaron (boson), and n is the concentration of
bipolaron. Eq. (35) is in agreement with the result of statistical physics 11).

From Eq. (34) for two-dimension we obtain12)

k T =π h n
B c ** s
(36)
m
where the n s
is the density of plane of bipolaron.

5. Calculation of superinsulating energy gap

Two years ago, the researcher, James Valles claimed to Have discovered Cooper
Pair in the superinsultators, that when cooled near absolute zero degree, offer infinite
resistance.........acting as perfect block conduction. And we have found that Cooper Pair
can be responsible not only for conducting electricity with zero resistance, but also for
blocking the flow of electricity altogether. Now, we calculate the condition from
superconductivity transfer to superinsulators.

Starting from Eq.( 32 ), under the superconducting condition, when T = Tc we request

∆k = 0 .
Under the superinsulating condition when T → 0 we request ∆ k
→ ∞ . In that case,
when T → 0 , we obtain

e
∆ k
=
e −1
µ = 1.582µ (37)

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This is the condition to transfer superconducting state to superinsulating state.

For two dimension, we have

∆ = 1.582π h n
k ** s
(38)
m
6. Discussion

From the description above we can see that in this theoretical frame work we can
calculate the superconducting critical temperature Tc and the condition from
superconducting state to transfer to superinsulating state at the same theory. So, this
is a unified theory of superconductivity and super insulation, indeed.

References:

1). Brown University Press Release, November 22, 2007.

“ Cooper Pair Found in Insulators as well as in Superconductors”
2). Nature 452(3 April 2008) 452-453.
3). http://en.wikipedia.org/wiki/Titanium_nitride
“Titanium Nitride”
4). W.P.Su ,J.Schriffer, A. Heeger, Phys. Rev. Lett. 42 (1979)698.
5). W.p.Su , J.Schriffer, A. Heeger, Phys.Rev. 22(1980)2099.
6). M.Born ,K. Huang, “Dynamical Theory of Crystal Lattice “
( Oxford Classic Texts in the Physics Science , 1954.
7). J. Callaway
“Quantum Theory of Solid State”. Academic Press, New York. 1991.
8). G.D.Mahan, “Many Particle Physics”, Plenum Press, New York, 1990.
9). A.L.Fetter ,J.Dirk Walec, “Quantum Theory of Many Particle System”
McGrownHill , New York, 1971.
10). Liang-you Zheng , Ying-Nan Chiu , Shan T., Lai, THEOCHEM, 680(2004) 37-39.
11). L.E.Reichl, “A Modern Course in Statistical Physics “University of Texas
Press 1980 ( Chater 9.4 ).
12). V.M. Loktev, Low Temp. Phys. 22 (1) ( 1996 )1.

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