945

Progress of Theoretical Physics, Vol. 31, No. 6, June 1964

Pauli Paramagnetism and Superconducting State

Kazumi MAKrt and Toshihiko TSUNETO*

Departnzent of Physics, Kyoto University, Kyoto

*Department of Physics, Faculty of Engineering Science
Osaka University, Toydnaka

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(Received January 27, 1964)
The effect of the Pauli paramagnetism on superconductors is discussed in detail. It is
shown that the· phase transition due to the paramagnetic effect changes its order from the
:first to the second as temperature increases. The modification of the mixed state in super-
conductors of the second kind is also discussed.

§ 1. Introduction
It has been pointed out by Clogston1 l and Chandrasekhar2 l that the critical
field of superconducting state is determined by the Pauli paramagnetism in some
superconductors of the second kind for which the ordinary upper critical field
Hc2 is larger than the field defined by
HP = L1a (T) /v/2 f1 (1)
where f1 is the Bohr magneton and L/0 (T) the energy gap 1n the absence of a
magnetic. field. This seems to be supported by the recent extensive investigation
of the high field superconductivity carried out by Hake and Berlincourt ;3) the
resistive critical fields of superconductors of the second kind are always smaller
than the smaller of Hc2 = V2~Hc and HP given by Eq. (1). The phase transition
in this case is generally believed to be of the first order.
In the present paper we would like to study in more detail the effect of
the spin paramagnetism on superconducting state on the basis of the current
microscopic theory. In the following two sections we shall carry through a
rather complete treatment of the effect due to the Pauli paramagnetism, assuming
1
! an external magnetic field to be uniform. A particular attention will be paid
to the thermodynamic behavior of a superconductor near the critical field in
·r
the whole temperature range. In § 4 we shall discuss the effect due to the
finite mean. free path, including the spin-orbit part of the interaction in the
impurity scattering. Section 5 is devoted to the problem of how the Abrikosov's
mixed state is modified by the paramagnetism.
§ 2. Formulation
As an extension of the discussion given by Clogston and Chandrasekhar,

i Present Address; Research Institute for Mathematical Sciences, Kyoto University:, Kyoto.
946 K. Mah and T. Tsuneto

we shall first formulate a theory of the superconducting-normal phase transition

which is induced by the Pauli paramagnetism. We start with the simplified
Hamil toni an of the form

H= __l_l (iV+eA)cjJ+(iV-eA)cjJdx+g\ (cjJ+cjJ) (cjJ+cjJ)dx+fJ.\cp+o-·HcjJdx. (2)

2m J J J
In the present section we neglect for simplicity the term involving the vector
·potential and assume that the magnetic field is constant throughout the specimen.
Although in ordinary bulk superconductors the diamagnetic term rather than

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the paramagnetic term plays an essential role in the transition due to a magnetic
field, it is still of interest to study this simplified model which is amenable to
a rather rigorous treatment. Besides, results obtained on this model seem to
be pertinent to the cases of a very small specimen where the diamagnetic effect
is practically negligible or of a superconductor of the second kind with a large
Ginzburg-Landau parameter /C.
The generalized Gor'kov equations which now include the Pauli term are
the following :
[iwn-~-fJ.(o-·H)]G(p) -iAF(p) =1,
(3)
[iwn+~--fJ.(o-·H)]F(p) +iAG(p) =0,
where G(p) and F(p) are the Fourier transform of the two Green's functions
defined by

G(x, x') = ( -i<TcfJt (x), cfJ; (x')) )

- i<TcfJJv (x), c/Jt (x')) ,
F(x, x') = ( <Tc/Jt (x), cfJJv (x')) )
(4)
<TcfJJv(x), c/Jt(x')) .

The gap parameter A is determined by the following equation :

A= g .. _1 ____ T~ f {Ftl (p) + FIA (p)} d 3p. (5)

2(2nY ~J " "1

Equations (3) are easily solved as

G( ) _ iwn- fJ. ( CF H) + ~
p - [iwn---'- fJ. (a-H) J2- ~ 2 - A2 '

(6)

Frmn Eq. (5) we obtain the equations to be used for lo':"er temperatures:
f'

ln (A/ Aoo) = -2 :f: (-l)n+

n"'l .
1
cosh n/}.H Ko (nA/T)
T
 Pauli Paramagnetism and Superconducting State 947

= _ j~2~T=e-CJ-pH)fT {1-t( ~)},for 11H<A,

= -j~nT ~ n- 112( -1)n+ 1 exp[ -n(A-!1H)/T], (7)

A n=l

for 11H =A,

where Aoo is the gap in the energy spectrum for H=O and T=0°K. On the
other hand, in the vicinity of the transition temperature we get
4
A V j;_ (p)
. -

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-In (T/Teo) -_ fo (p) + 21 ( 2nT) A ) j; (p)'
S3 ( 2nT (8)

where Teo is the transition temperature for H = 0 and is equal to Teo= r Aoo/ n,
and

(9)

(10)

00

f2(p) =R~~ n+ 1 + ip ) -5 ,
(

2
(11)
"··ith p = (!1H/2nT) and ¢ (x) = T' (x) I r (x)' the di-Gamma function.
Using A determined in this way, we can calculate the free energy as well
as the magnetic ·susceptibility of the system. Before going into the caLcu-
lation of the free energy and the discussion of the behavior of the system near
the transition point, let us first examine the lower instability limit of the magnetic
field below which the normal state becomes unstable against the formation of
condensed pairs. This critical field, which is indeed the usual thermodynamical
critical field if the transition is actually of the second order, is given simply
by putting A= 0 in Eq. (7) or

(12)

vvith t = T /Teo· The asymptotic solutions are

In (2!1Hc/ Aoo) = (1/24) (2nT/ !1HeY for T <Teo, (13)
-In t = 7 ( (3) p/ for p<l. (14)

The dependence of the critical field on temperature calculated numerically IS

depicted in Fig. 1.
The most remarkable feature is that this field is not monotonously decreasing
function of the reduced temperature t but has a maximum around t=0.5. This
behavior can be seen more directly if we rewrite Eq. (12) as
948 K. Maki and T. Tsuneto

(15)

in terms of the statistical function

(fJ (T ~) =tanh ~ + fJ.H +tanh~- /1H

H ' 2T 2T
which represents the probability of a pair of quasi-particles with opposite mo-
menta and ~pins being present at temperature T.

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We shall see in the next section that the phase transition is indeed of the
second order for t larger than to= 0.556 so that the field obtained here is in
fact the critical field in this temperature region. For smaller values of t the
transition becomes one of the first order and the critical field is much larger
than the above field : The latter then gives the supercooling critical field.

§ 3. Free energy and order of phase transition

The free energy can be calculated by means of the formula
d

Fs-Fn= \ d(1/Jgj)J\ (16)

"0
where
d(1/Jgj) = - (mpo/2n 2.:1oo)d.:lao. (17)
For lower temperatures we obtain from Eq. (7)

d (1/Jgl) = _!!!d>_o__
2rr 2
1
{- - - + 2:f: ( -1)n+ 1 cosh ( njJ.H) __!!_ Ko'
.:1 n=l T T
(!!A)}
T
d.:J. (18)

Substituting this expression into (16) we get

co

+ zi: (-1)n+l cosh (_!l_fJ.H)

n=l T
T2
n
2
\
"
K 1 (x) x 2 dx} , (19)
nd/T

where we have made use of the relation

nd/T oo

\ 2
K1 (x) x dx= 2- \ K1 (x) x 2dx.
"0 "nd/T
 Pauli Paramagnetism and Superconducting State 949

When J/T';P 1, the above equation reduces to

F -F
s n
= mpoT2- mpo
6 2n 2
{L-
2
(fJ.HY+_l---v2nL1o2T(1+--~~ _I_)e-<J-,..H>;r}
2 8 L1
(20)
The transition point Is determined by F 8 - Fn = 0. Solving this we find for the
critical field

which reduces at T = 0 to the expression (1) given by Clogston. For higher

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temperatures we obtain from Eq. (8)

d(1/l J) =- mpo{t;C) J - 3 +() Ja }dJ (22)

g 2n
2 1
P (2nTY 2-J 2 P (2nTY
and for the free energy
F 8 - F - - mpo { 1 f 1( ) J4 (23)
n- 2n 2 4 P (2nTY

When T is close to Teo and (J/2nTY

is small, one sees that the condition
Fs- Fn = 0 leads to J 2 = 0. Consequently,
the phase transition is of the second
order at higher temperatures, while \Ve
0.25 have seen just above that it is of the
first order near T= 0. Therefore, the
order of the phase transition should
change from the first to the second as
0~----------~~----------~ temperature increases.
0 0.5 1.0
t In the region where the transition
Fig. 1. The H- T phase diagram. The solid is of the first order, the solution of the
curve is the critical field of the second
gap equation is double valued, one of
order transition determined by Eq. (12),
and the dotted line is that of the first the branch vanishing at the lower curve
order transition (F8 -Fn) =0. Above of Fig. 1 and another corresponding
the critical point (t0 =0.556), the transi- to the actual gap. (For more accurate
tion is of the second order. For t< t 0 ,
analysis of the gap solution, see Ap-
the solid curve gives the supercooling
critical field. pendix.)
We can apply to the present prob-
lem the general discussion of the change of the order of the transition which
is given by Landau and Lifshitz. 4 l The cirtical point at which the order
changes is characterized by the value of p which is defined by j;_ (p) = 0. The
function j;_ (p) is a monotonously decreasing function of p, so it is easy to find
the zero of j;_ (p): we find Po= 0.308. While for p smaller than Po (or t>to =
0.556) j;_ (p) is positive and the phase transition is of the second order, for p
950 K. Maki and T. Tsuneto

larger than Po the phase transition becomes of the first order. When p is slightly
larger than Po, the ratio f1 (p) /f2 (p) is small and Lie at the first order transition
point is determined by . (Lic/nTY = f1 (p) /j; (p). In this region we have ap-
proximately
fo(P) =0.566+2.83x,

~(p) = -2.19x+80x 2, (24)

f2 (p) = -13.2 + 13.9x,

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where x = p- Po, so that
(Lic/rcTY = (2.19x- 80x 2) (13.2 -13.9x) -I, (25)
t = exp (- 0.566- 2.83x + 4.5x 2) . (26)
With the help of the above equations we can calculate the phase diagram, which
is also shown in Fig. 1.
Incidentally, we note that the critical point f1 (p) = 0 is also the branch
point for the gap solution.
From the general theory of the second order transition we know that dH/ dT
is continuous along the transition curve but d 2H/ dT 2 has a gap at the critical
point : This gap is equal to .

.d 2H/dT 2 Ito+o -!to-o= 0.402_1__ . (27)

To
Finally, it is interesting to note the behavior of the specific heat close to HP
at t~t 0 , especially its jump at the transition temperature for a given magnetic
field H. At t not too far from t1 we have from Eq. (8)

(28)

where
a=- (1 + Pfo' (p)) T1- 1=- 0.11 T1- 1.

Eliminating Ll by means of this relation one can calculate the specific heat and
herice its jump at T1. In the case T1 is not too close to To so that f1 =;i=O and
the first term in the free energy is larger than the second, we get

F - F = - mpo (2nT) 2 4a2 (T - T) 2 +" -· 1 (29)

8 n 2 C2nY 1 J 1 ,

and the specific heat jump is equal to

LIC8 = 4mpo T1 3 a 2 f1- 1,..._,0.073nzpoT1 2 (To- T1) - 1. (30)
For T1 very close to T 0 , we have ~(PrJ = 0 and
8
~ (T - T))
312
F - F = - _!!_Y?_(l__ (2nT) 2 ( - (- +) - 1;2 (31)
8 n 2 (2nY . 3 1 J 2 ,,
 Pauli Paramagnetism and Supercondu~ting State 951

LlCs = 2 v·2)3mpo T1 s (-a Y12 (- j;) - 112 (To- T 1) - 112

""0.016mp 0 T1s 12 (To- T1) - 112 . (32)
Thus, the jump in the specific heat increases indefinitely along the transition
curve towards the critical point.

§ 4. Effects of finite mean free path

The electronic mean free path is expected to be very short in the su-

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perconductors for which the Pauli paramagnetism is important. It is important,
therefore, to see whether the results obtained in the above sections is modified
by the effect of. the .short mean free path or not. For this purpose, following
Abrikosov and Gor'kov/) we assume that the amplitude for the scattering of
an electron by an impurity atom can be written in the following form which
includes the spin-orbit interaction:
f(p, p') =a(p, p') +ib(p, p')Pu- 2 ([p, p']a-) (33)
where p and p' are the momenta of the electron before and· after the collision,
a- the Pauli spin matrix and Po the Fermi momentum. The standard method
of treating in1purity scattering enables tis to arrive at the following expressiOns
for the two Green's functions :

(34)

(35)

and
_1_= nm~
2
\dQ(/a/2+ /b/2 sin20) =-1-+_l__'
r 4n ,} • ro r1
_"!___ = _!!__mPo \ dQ ib /2 sin2 (}. (36)
r1 4n 2 J
The terms with 1/rl come from the spin-orbit interaction : 1/rl is usually small
compared to 1/r0 •
Let us first consider the case where 1/r1 = 0. Since no m1xmg of electrons
with different spms occurs in this case, Eq. (35) can easily be solved;
(37)
where
(38)
952 K. Maki and T. Tsuneto

From this it is easy to show that the results obtained for the case where 1/r = 0
remain valid without any change also in the case where 1/r=FO, the conclusion
which is consistent with the theory of the Knight shift given by Abrikosov and
Gor'kov. 5 >
When the spin-orbit interaction is present, the mixing of the different spin
states is possible and the superconducting state has a finite Pauli paramagnetism
even at T = 0° K. Therefore, the critical field must be higher than that in the
case where 1/r1 = 0. For the following discussion it is more convenient to re-
write Eq. (35) in the form

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(w ± ifJ.H) / L1 = u± + (3r 1.:1) - 1(u±-u+) (1 + u/) - 112 (39)
where u± = w±/X±. This equation is clearly too complicated to allow a general
solution. In the limit of vanishing L1 we can solve Eq. (35) and obtain
u± = L1 (Cvn ± ijJ.H (wn =f ifJ.H) (wn =f i11H + 2/3r 1) - 1+ 0.:1 2). ( 40)
If the phase transition is of the second order, the critical field is determined
by the usual gap equation which now reduces to

1 =- gmp_o_ 2nT ~ (~ +-1-) . (41)

2 (2nY ron<"'n Un+ Un-

This can be rewritten as

-In t = t{ n + 1/2 + (3r1nT) -

1
_ 1 }
n=o (n + 1/2Y + (3r1nT)- 1(n + 1/2) + (fJ.H/2nTi n + 1/2

= ~ {y0( ~ + p_) + y0( ~ + P+) + (1- (3r1fJ.HY) - 112

where

P± =_l---(-
1
2nT 3r1
±j~-
9r1
(flHY). (43)

Close to the transition temperature where (!LH/2nTY~1 we obtain

-In t = (fJ.H/2nTY7t;, (3) x (1;'3r1nT), (44)
with
1
x(a) = - - - -
00
1
~---- - - - -
1
(45)
7 ( (3) n=o (n + 1/2Y n + 1/2 +a
When the mean free path with spin flipping is short, 1.e.
is much simplified :

(46)
 Pauli Paramagnetism and Superconducting State 953

where
( = 3-rl (fJ.H)2 ( 4nT) -l .
It must be emphasized here that in this limit the phase transition is always of
the second order independent of temperature. We also note that other effects
such as orbital paramagnetism are not important for the phase transition.

§ 5. Modification of Ahrikosov~s mixed state

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In superconductors of the second kind for which HP defined by Eq. (1) is
comparable with or smaller than. the so-called upper critical field Hc 2 , we expect
properties of the Abrikosov's mixed state 6 > to be considerably affected by the
Pauli paramagnetism. In order to discuss this problem we shall first incorporate
the paramagnetic term into the Ginzburg-La~dau equation.
In deriving the G-L equation from the Gor'kov equation we first note the
fact that the spin correlation of electrons in the normal state extends over the
distance of the order of 1/Po, which is much smaller than the penetration depth.
Therefore, in the derivation we may consider the magnetic field to be constant,
equal to a local value H(x), in the Pauli term. According to Gor'kov 7> the
quantities to be calculated are

\Ka(R)dR and \Ka(R)R2dR,

oJ oJ

where the Fourier component of Ko (R) IS giVen by

K(q) =_2n~-L:
(2n) n
J. UJ)n-
1
jJ.H- ~ P
.
UJ)n-
1 _dap
jJ.H + ~ p+q

~ ;~o-nr~JdQLwn!/1H __7)_9f~ (iwn~/1-HY

+ (voqzY 1 } (47)
4 (iwn- 11HY + ... .
If one neglects the terms of the order (fJ.H/nTY, which is small at temperatures
close to Tc, the only non-vanishing effect turns out to be the correction to JKo (R) dR.
In this way we can easily derive the modified G-L equation:
3
{-l(V+2ieA(x)Y+-l_[ Tc-T _ _Z(( ) CI.J(x) I +2(11HY)]}L1(x) =0.
2

4m A Tc 8 (nTcY
(48)
Although we have derived this equation for a pure superconductor, it is not
difficult to see from the discussion given in § 4 that the equation of the same
form holds also for the case of short mean free path with the appropriate change
of the G-L parameter JG (if the spin-orbit coupling is absent). In order to
discuss the mixed state we write the G-L equation in the familiar form:
954 K. Maki and T. Tsuneto

(49)

and

-curl curl A= 1¢1 2 A+ ~t~ (¢·'r-V¢- <}IV¢*)

2/C
- r curl (HI¢1 2
), (50)
where

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r= 2
4,u H/ _ 8m,Po (l _ ___I_) ,u2. (51)
L1 2 n Tc
It is possible, fortunately, to obtain the solution for the mixed state from our
modified equations. The upper critical field is readily seen to be
(52)
where

a 2 = (2r) - l C~/1 + 4~C r -1).

2
(53)
The magnetic field to the first order in 1¢1 2 is now given by
H = Ho- (2/C) - l (1 + 2ra 2 ) 1¢1 2 • (54)
One can carry out the same calculation as given by Abrikosov with the result

(55)

with
and (56)
The magnetization and the free energy are given by
B= H = Ho- (a 2I IC- Ho) I (21C' 2 -1) (3 (57)
and

respectively. It is seen that the effect of the Pauli paramagnetism is to reduce

the parameter /C. We emphasize that when IC'>llv2, the phase transition to
the normal state is always of the second order, the real upper critical field
now being given by Eq. (52). Obviously the lower critical field is hardly changed
by the paramagnetism.
, We can compare Eq. (52) for the upper critical field with the experimental
data obtained by Hake and Berlincourt. 3 ) Equation (52) may be written in a
more convenient form
 Pauli Paramagnetism and Superconducting State 955

(59)
where Hv and He/ are the field given by
240 (1) and the usual upper critical field deter-
(kG)
m~ned by /C. The theoretical values are
plotted in Fig. 2 for Ti-V alloys together
with HP and He/ and the resistive critical
field Hr given by Hake and Berlincourt.
120 The theoretical values are consistently below

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Hr. The discrepancy may be due to the fact
that the experimental data are taken at T=
1.2° K which is much too low for our
theory to be quantitatively reliable. It must
0 20 40 60 80 100 also be pointed out that the spin-orbit interac-
Atomic percent V tion, which may well be important for the
Fig. 2. The theoretical upper critical alloys in question, would effectively enhance
field, Eq. (59), is compared with
the upper critical field.
the data for Ti-V alloys given in
reference 3), Fig. 13. He/, EP and
Hr are, respectively'v2 KHe, Jjy'2p, § 6. Concluding remarks
and the resistive critical field.
The most interesting result of our
analysis is that the order of the phase transition due to the Pauli paramagne-
tism changes from the first to the second as temperature increases. Although
. we have obtained this result with a siwplified rriodel, we would think that the
main feature remains the same for a more realistic case. In this respect it
would be particularly desirable to have more accurate experimental data con-
cerning the various properties of superconductors of the second kind possessing
relatively small Hv, such as the upper critical field at all temperatures and
the specific heat jump along the transition curve. One of the theoretical prob-
lems to be solved is to extend our discussion of the mixed state to the case
where the transition becomes of the first order, a situation expected to occur
at lower temperatures in a superconductor with HP<He/.

Acknowledgn;Ients

One of the authors (T.T.) should like to thank Prof. T. Matsubara for his
kind hospitality given to him· during the course of this work.

Appendix

It 1s interesting to see more explicitly the behavior of the solution of the

gap equation (5) in the region of temperature where the transition is of the
first order. Let us find out where the branch line o{ the solution lies in the
H- T plane, which is determined by solving
956 K. Maki and T. Tsuneto

a (the gap equation) = 0 (A·l)

aLl
together with the gap equation. For tempera-
tures close to 0° K we can use the second equa-
tion of (7). The asymptotic form of the branch
line is given by
j = Lloo exp ( - T / Ll) ,

JJ.H = Ll- T ln V'2nLI/T. (A·2)

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Hence, at T = 0° K, JJ.H = L/ 00 • Close to the
branch point the gap solutions are given by
0.5
Fig. 3. The branch line of the
solution of the gap equation. where Ll1 and H1 are the gap and the field at
the branch point. In the vicinity of the critical
point T= T 0 , we can use Eq. (8) and obtain

(LI/2nTY = __J,___J;. (p) /f2 (p),

3

T/Tco=exp[ -fo(P) -+ ~ 2 (p)jj;(p) J. (A·4)

The branch line terminates at the critical point. In Fig. 3 we present in a

schematic way the branch line in the H-T diagram. The curves, A-D and
B-D, are the solutions of Eq. (12) and Fs- Fn = 0, respectively. In the region
enclosed by the line C-D--A there exist two positive solutions for the gap L1 in
addition to the trivial solution, one of which vanishes at the line A-D. The
branch line C-D may be interpreted as the superheating critical field.

References

1) A. M. Clogston, Phys. Rev. Letters 9 (1962), 266.

2) B. S. Chandrasekhar, Appl. Phys. Letters 1 (1962), 7.
3) R. R. Hake and T. G. Berlincourt, Phys. Rev. 131 (1963), 140.
4) L. D. Landau and E. M. Lifshitz, Statistical Physics (English translation, Pergamon
Press, 1958).
5) A. A. Abrikosov and L. P. Gor'kov, ZETF 42 (1962), 1088.
6) A. A. Abrikosov, ZETF 32 (1957), 1442.
7) L. P. Gor'kov, ZETF 36 (1959), 1918.