Calculation of Critical Temperature Tc in High

Temperature Superconductivity
Using Grand Canonical Ensemble

Liang-You Zheng, Ying-Nan Chiu*, and Shan T. Lai†

Center for Molecular Dynamics and Energy Transfer,

Department of Chemistry, the Catholic University of America, Washington, DC, 20064
USA

* Also Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei,

Taiwan, R.O.C.
† Vitreous State Laboratory, The Catholic University of America, Washington, DC
20064, USA, E-mail: shantaol@vsl.cua.edu

1
Abstract

In this paper we use the grand canonical ensemble to calculate the Tc of

superconductivity for the compound Yba2Cu3O7 under one dimensional Cu-O chain
model. The results are consistent with experiments.

1. Introduction

In the previous paper [1], we have proposed two sites small bipolaron model
in one-dimension Cu-O chain for the compound YBa2Cu3O7 to obtain a
diagonalized Hamiltonian.

H$ = ∑ [ E
k
0
( k ) − ∆k] C
$k ( o+
C$ + C$ C$ ) + ∑ E (a$ a$
o

k
e+

k
e

k
q
q
+
q q
1
+ ).
2
(1)

Here
E 0
( k ) = −2 t 0 cos( 2πka ) , ( 1.1 )

B k ,q
∆ k
=∑
q hω q
, ( 1.2 )

and

(i 2πqa) ,
h
B = 2γ cos( 2πka ) ( 1.3 )
k ,q
2 NM ω q

E q
= hω q . ( 1.4 )

Now, we rewrite the form of Hamiltonian as follows

 1
H$ = ∑ E n$ + ∑ E  n$
k
k k
q
q q
+  ,
2
( 1.5 )

E k
= E 0
( k ) − ∆k , (1.6)
and
o+ o e+ e + +
n$ = n$ + n$ = C$ C$ + C$ C$ = B$ B n$ = a$ a$
o e
k k k k k k k k k
, q q q
. (1.7)

2
2. Calculation of Tc
We will make a calculation of Tc starting from Eq.(1.5) for compound
Yba2Cu3O7. 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 Z g according to the definition of grand partition function

  
Z = Tr exp − β  ˆ − µ ˆ  , ( 2.1 )
g
  H N 

Here
H$ the Hamiltonian of boson particle gas i.e. the Eq. (1.5)

N$ 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 , ( 2.2 )

and then according to the definition we can calculate the total number of
particles
∂Ω
N =− , (2.3)
∂µ
and the Helmholtz free energy is as follows

F = Ω + µN . (2.4)

Using the stability condition of superconducting system

∂F
∂ ∆k ∆k
δF = δ =0, (2.5)

we obtain the equation of satisfaction of relationship between

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

3
 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 ....... (2.5)

According to the definition of grand partition function

 
−β  H$ −µ N$ 
Z g = Tr e  

=∑ {n } exp− β  H$ − µ N$   {n } , (2.6)

{n }
in occupation representation, the operators of above equation can be replaced
by their eigenvalues. So we have the Zg [2]

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

 
∑ {n } exp − β  ∑ ( E ) n   {n }

= k k
−µ k k
×
{n } k
 k 

∑ {n } {n }
   1  
× exp − β  ∑ E q  nq +   
  q  2   
{n }
q q
q

[ (E )n ] n
∞ ∞ ∞
= ∑ n k1
exp − β k1
−µ k1 k1
× ∑ ......... ∑ ...........×
n k 1= 0 nk 2 n ki

∞ ∞ ∞
  1 
×∑ n exp − β E q1  nq1 +   nq1 × ∑ ........× ∑ ..........
q1
  2 
nq 1 nq 2 = 0 nqi = 0

1 1
= Πk
1 − exp − β (ε k − ∆k [ )] Π q
1 − exp − β ( E ), q
(2.7)

where ε k
= E 0
(k) − µ .

4
If we use the following relation

∑ exp[− β (ε − ∆k )nki ]
∞

ik
n =0

[ ] [ ] [ ]
ki

= exp − β (ε ki − ∆k )× 0 + exp − β (ε ki − ∆ki )× 1 + exp − β (ε ki − ∆ki )× 2 + ......

1 1
= 1 + x + x + x +............ =
2 3
=
[ ( )]

1 − x 1 − exp − β
ε k ∆k
−

from Eqs. (2.2), (2.3), (2.4), (2.7) we obtain

µβ exp{− β (ε k − ∆k )} = exp{− β (ε k − ∆ k )} − 1 . (2.8)

This is the equation of relationship between superconducting energy gap and

temperature.

When T=Tc, we request ∆ k

= 0 ,Therefore, we have

µ β exp{− β ε } = exp{− β ε } − 1
c c
k k
(2.9)
c c c

This is the transcendental equation. Here β =

1
, ε
c
= E (k) − µ
c
k T B c
k 0

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

Eq. (2.9) we obtain

µ
T = (2.10)
c
k B

According to mean field theory [3], if we take t0=0.25eV , then µ = 0.00833eV [4]
we can obtain
T c = 96.6K ( 2.11 )

This theoretical result is agreement with experiment.

After considering the modification of with temperature, from Eq. (2.10) we have

k T = 3.31 h n
2

B c ∗∗
3 (2.12)
m

5
 ∗∗
where m is the mass of bipolaron ( boson ), and n is the concentration of
bipolaron ( boson ). Eq. (2.11) is agreement with the result of statistical physics [5].

From Esq. (2.10) for 2-Dimensional Cu – O plan we obtain

k T =π h n
B c ∗∗ S
, (2.13)
m
where the n S
is the density of plane bipolaron [6] .

To test the correctness of Eq.( 2.10 ), we directly solve Eq. ( 2.9 ) by using
Newton’s iterative method and taking BASIC language of computer program[7].
The result is the same as Eq. ( 2.11 ).

ACKNOWLEDGEMENTS

This work is supported in part by NL Chemical Technology Inc. and Theoretical

Research Fund and in part by Chiu Feng-Chia Research Fund.

6
Appendix A:

Here, we calculate the Fermi energy EF for the compound Yba2Cu3O7.

According to V. Z. Kresin and S. A. Wolf [8]

p F
= 2πhnab ( A.1 )

( i.e. Eq.(9) in Kresin’s book )

Here p F
is Fermi momentum of electron, h is Planck constant, a is
the interlayer distance, b is the distance between neighboring chain ( within one
layer ), n is the usual volume concentration of electron.

h = 1.054 × 10 − 27 erg.sec.
−3
n = 5 × 10 21 cm

 11671
. 
b = 3.817 A = 3.817 × 10 − 8 cm a=  × 2 = 38903
0 0

 6 
. A

We obtain p = 4.91 × 10−20 g .cm / sec ( A.2 )

F

2
p
Since E =2 F
F
∗ , ( A.3 )
m
∗
= 9.1 × 10−28 g
*
and m is effective mass of electron , m = 100 me , me

Substituting them into Eq. (A3), we obtain

E F = 0.00833eV ( A.4 )
That is chemical potential µ =0.00833eV in formula ( 2.10 ).

7
Appendix B: Use Newton’s iterative method to solve Eq. ( 2.9 )

We rewrite Eq.( 2.9 ) as follows

bx e = e − 1
ax ax
( B.1 )

f ( x ) = 1 + ( bx − 1) e
ax
We define ( B.2 )

The first derivative f ′( x ) = (b + a (bx − 1))e ax ( B.3 )

= −h = −
f (x )
n
x n +1 x n x n
f ′( x )
( B.4 )
n

The BASIC computer program is as follows

10 READ b, a, x 0
20 FOR n=0 TO 5

(1 + (b ∗ x(n ) − 1)) ∗ ea∗x (n )

30 h=
((b + a ∗ (b ∗ x(n ) − 1))) ∗ ea∗x (n )

40 x( 0) = 120

50 x( n + 1) = x( n) − h
60 NEXT n
70 DATA 0.00833, 0.99167, 120

1
80 PRINT n, h, x ( n ) ,
x( n)

 1 
  ∗1.6 E − 12
 x ( n) 
90 T c = 1.38 E − 16
100 PRINT T c

110 END

8
References:

[1] Liang-You Zheng, Ying-Nan Chiu, Xing-Cai Xiao, P. Palting, Shan T. Lai,
Journal of Molecular Structure( Theochem) 572(2001)1-4.
[2] Alexander L. Fetter, John Dirk Walecka, “Quantum Theory of Many-Particle
System “, McGraw-Hill Book Company 1971.
[3] Andrei E. Ruckenstein et al. Phys.Rev. B Vol.36, No.1 ( 1 July , 1987 )857.
[4] Appendix A
[5] L.E.Reichl, “ A Modern Course in Statistical Physics “, Chapter 9.4
University of Texas Press , 1980.
[6] V.M.Loktev, Low Temp. Phys. 22(1)(1996)1.
[7] Appendix B
[8] Edited by V.Z. Kresin and S.A. Wolf, “ Novel Superconductivity “ P.289
Plenum Press. New York and London, 1987.