International Journal of Advances in Science and Technology,

Vol. 4, No.2, 2012

Vibrational Pseudospin Solution (Triglycine Sulphate
Crystal) For Computing Technology

T.C. Upadhyay
1
and Ashish Nautiyal
2
1
Department of Physics, H.N.B. Garhwal University, Uttarakhand, India-246174
andehradun@yahoomail.com

2
Department of Physics, H.N.B. Garhwal University, Uttarakhand, India-246174
ashishphysics@yahoomail.com
Abstract

The importance of vibration pseudospin solution of ferroelectric (triglycine sulphate (TGS))
crystal in computing technology have been studied by a combined theoretical model pseudospin
lattice coupled mode (PLCM) and Ising spin model of ferroelectrics for second order phase
transition with renormalized boundary condition of polarization. These two theories have been
developed with third and fourth order phonon anharmonic interaction terms as well as electric field
terms. We have discussed dielectric, electric, acoustic and photosensitive properties of the crystal in
better pseudospin transition between double potential well. Model can easily be extended for lower
as well as higher order anharmonic interactions of lattices. With these properties we have predicted
the possible application of triglycine sulphate crystal in computing (memory) device.

Keywords: lattice vibration1, pseudospin2, ferroelectrics3, pyroelectrics4, nonvolatile memory5.

1. Introduction

Triglycine sulphate (TGS)[1] crystal is a hydrogen bonded pyroelectric order -disorder type
crystal whose chemical formation is {3HN
2
CH
2
COOH+H
2
SO
4
(NH
2
CH
2
COOH)
3
H
2
SO
4
} in
which (NH
2
CH
2
COOH)
3
H
2
SO
4
indicate three different form of glycine ions (glycineI, glycineII
and glycineIII ions). Triglycine sulphate is a monoclinic, centrio symmetric crystal with space
group points 2m, 2, which disappear after the phase transition. Phase transition is process at
which, crystal transform its ferroelectric phase into paraelectric phase means polar state to non
polar state at a particular temperature 49
0
C which is known as curies temperature of crystal.
This phase transition is a second order phase transition wi th renormalized boundary condition of
polarization. Quantum tunneling of a proton between glycineII and glycineIII with mirror
symmetry (hydrogen bond) proposed a pseudo spin behaviour of the TGS crystal. We have
taken this pseudo spin behaviour of crystal, as the main key source of the crystal behaviors. On
the bases of this property we have chosen two theoretical models i.e. PLCM and Ising spin
models [2, 3] which are implemented over TGS crystal perfectly by the help of double time,
temperature Greens function [4] method. By this method we evaluate different values i.e.
differentiability (smooth function) and relaxation time of TGS crystal even in external biasing.
We also discuss about the technological (computing) importance of TGS crystal with best
experimental data support [5, 6].

2. Vibrational pseudospin solution

We consider the Green's function
) (
1
); (
1
) ( t
z
j
S t
z
i
S t t
ij
G ' = '


(

' ' u = ) t (
z
j 1
S ); t (
z
i 1
S ) t t ( i
, (1)
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Where = 1, [S
Z
1i,
S
Z
1j
]

= S
Z
1i
S
Z
1j
- S
Z
1i
S
Z
1j
]
(t) = 1 for t >0
=0 for t < 0
Angular bracket <-----> denotes ensemble average over a grand canonical ensemble. It follows from
the definition that the Greens functions so defined are a function of t-t only. The fourier-transformed
Greens function is defined by
G
ij
(t-t)=<< S
Z
1i
S
Z
1j
>> = dt e t G
t i
ij
e
}

H
) (
2
1

This Greens function satisfies the equation of motion
S ] S , [S > ] S , S [
2
1
= >> S , S <<
z
1j
z
1j
z
1i
z
1j
z
1i
z
1j
z
1i e q e
e >> << + <
[

The equation for
e
>> <<
Z
J
Z
I
S S
1 1
, , thus involves and in-homogenous terms and higher-order Greens
function. One of the problem of this method is to decoupled the higher-order Greens function and
choose appropriate Greens function so that a closed system of equation is obtained.
In addition we have shown that the poles of the Green function correspond to the energies of the
elementary excitation of the system. The average value of the product of two operators can be
calculated from the formula.
<S
}

>> << >> <<

>= < e
q
e e
e
d S S S S i
e
S S
ie
z
j
z
i ie
z
j
z
i
i
t
z
j
z
i
) (
) (
1
,
1 1 1 1
0
1 1 lim
>
The parameter may be arbitrarily chosen as +1 or -1. If
z
i
S
1
and
z
j
S
1
are bose operators, is
generally chosen as +1 and if they are Fermi operators, is chosen to be -1. Sometimes however, the
reverse choice become necessary. In the problem of TGS (Triglycine Sulphate) crystal, where one
deals with spin operators. It would be convenient to chosen = +. Since world simplify the in-
homogenous terms in above mentioned equation considerderably. However it turns out that Greens
function for system have a zero frequency pole. Under these consideration, in the calculation for which
= +1, can not be used. Since the integral becomes divergent (efforts to circumstances this problem
by the addition of vanishingly small perturbation terms were unsuccessful) on therefore has to resort to
fermion Greens function i.e. with = -1, to treat the pseudo spin problem.
>> << O > + >>=< <<
+ + + +
f g g f fg g f f g
S S S S S S S S 2 ) 2 1 ( o e
( )

>> < < + >> << +
+ + + +
m
f g l
l
f m g gm
S S S J S S S J
lg
2
1
) (
2
1

>> << >> << O

H
> <
>>= <<
+ +

+
m
f m g gm f g
g f
f g
S S S J S S
S S
S S
2
1
2
2
2
e

>> <<
+
l
f g l
S S S J
lg
2
1

>> << O + >> << O
H

>>= <<
+
+
+
f g f g
g f fg
f g
S S S S
S S
S S
2
) )( 1 ( o
e
The above equation can be closed by decoupling the higher order Greens functions. The two
decoupling procedure.
In decoupling of pseudospin, one assumes that
>> ><< >>=< <<
+ +
f g
g
m f
z
m g
S S S S S S
>> ><< >>=< <<
+ +
f g
z
l f g
z
l
S S S S S S
Introduce the notation
February Issue Page 76 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

x= <S
x
> = <S
y
>, n = <S
z
>,

=
j
ij
J J
0

Then the above equation of decoupling becomes as, if f=g
|
|
|
.
|

\
|
H
=
|
|
|
.
|

\
|
>> <<
>> <<
>> + <<
|
|
|
.
|

\
|
O O
O +
O
0
0
1
2
1
2 0
2 0
0
0
z
n J
n J
e
e
e

Where <<+- >>,<< -- >>,<< z- >> are aberration of notation for >> <<
+
f f
S S etc.
The secular determinant for the system is given by
2 2
(
p
e e e = A )
Where,
2
1
2 2
0
)] ) 2 ( ) [(( O + = m J
p
e (2)
From above mentioned equation
] 2 ) ( )[
2
1
(
2
0
O + >>= + << n J e e
spontaneous polarization in TGS crystal is
P
s
=2N

<s
z
>
In two dimensional form of pseudospin in z-directional sum is not zero before T
C
(Curie temperature).
S
1
Z
+ S
1
Z
0;
And S
1
Z
S
1
Z
; For T<T
C
,
But after curie temperature total spontaneous polarization become zero.
S
1
Z
+ S
1
Z
=0; For T>T
C,
Specially for TGS crystal (ferroelectric) both spin become zero.
S
1
Z
= S
1
Z
= 0; For TGS (ferroelectric crystal) crystal at phase transition,
while S
1
Z
; S
1
Z
>0; but P
S
0 not exactly zero.(for second order phase transition)
)
2
~
tanh(
~
O
O
O
>= <
|
x
S
0 >= <
y
S
)
2
~
tanh(
~
2
) (
3 '
0 0
O
O
> < + > <
>= <
|
Z Z
z
S J S J
S
Differentiated twice GF(2) first with respect to time(t) and then with respect to time (t') using model
Hamiltonian (Eq.1) taking Fourier transformation and setting it into Dyson's equation from
( ) ( ) ( ) ( ) ( ) e e e e e
0 0 0
ij ij ij ij
G P G G G + =
(3)
Where,
( )
( )
2 2
1
0
4O
O
=
e t
o
e
ij
x
i
ij
S
G
(4)
( )
( ) ( ) e e t
e
P
S
G
x
i
ij
O
O
=
2 2
1
4
(5)
Where,
), (
~
~
) (
~
) ( e e e P P P + = (6)
February Issue Page 77 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

y
ij
t
i
x
i
S F
S
i
P ; ) (
~
) (
2
1
O
=
t
e (7)
j i
x
i
F F
S
P , ) (
~
~
2
1
2
2
O
=
t
e (8)
The second term of Eq. (6) contains higher order Green's functions which are decoupled by using
scheme <abcd>=<ab><cd>+<ac><bd>+<ad><bc>. Then simpler Green's functions are solved in
the zeroth order approximation i.e. higher order terms are neglected from ) (e P type terms. In Eq.(8)
) (
~
~
e P is resolved into its real and imaginary parts using formula
( ) x i
x
1
im x
1
lim
0 m
to
|
|
.
|

\
|
=
+

.
The real part is known as shift ) (e A and the imaginary part is called width ) (e I .
These are obtained as following
Spin shift is
( ) ( ) ( )
2 2
2 2 2
2 2
2 2 2 2
2 2
4
~
2
4
~
2
~
4
~
2
) (
O O
+
O O
+
O O
+
O O
= A
e

e e
e
a E a N V c b a
k ik
s
(9)
( )
( )
( )
(

I + |
.
|

\
|
O
) (
= A

e e e
e e o e
e
2 2
2
2 2
2 2
1
2
4
~
~
~
~
2
k k k
k
kk
k
x
i ik
p s
i
S V
(10)
Spin width is
( ) ( ) ( ) | | O + O
O O
= I
~ ~
~
4
4
e o e o
t
e
a

( ) ( ) | | O + O
O O
+
~ ~
~
4
2 2
e e o
c b

+ ( ) ( ) | | O + O
O O
~ ~
~
4
2 2
e o e o
a N V
k ik

+ ( ) ( ) | | O + O
O O
~ ~
~
4
2
2 2 2
e o e o
t a E
, (11)
Spin Phonon width is
( )
( )
( ) ( )
(

I +
) (
= I

e e e e
e e e
e
2 2
2
2 2
2 2
1
2
4
~
~
~
~
4
k k k
k k
x
i ik
p s
S V
(12)
In Eq.(10) and (12)
k
e
~
~
is renormalized phonon frequency and ) (e
k
I is phonon width in the Green's
function >> =<< ) ' ( ); ( ) ' (
1
'
t A t A t t G
k
k kk
which are obtained as

( )
( ) ( ) | | e e e e e t
o e
e
I + A
=
i
G
k k k
kk k
ij
{ 2
~
~2 2
'
'
(13)
( ) e e e e
k k k k
A + = 2
~
~
~ 2 2
, (14.1)
Phonon shift is given as
February Issue Page 78 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

( ) ( )
( )
2
2 1
) 3 (
2
, , 18
Re
1
k k k V P
P
k k
k k
=
= A

e e


( )
( )
( )
( )
)
`

e + e e
e + e
+

e + e e
e + e
+
e e
e e
2
2 k 1 k
2
2 k 1 k
k k
2
2 k 1 k
2
2 k 1 k
2 k 1 k
2 k 1 k
2 k 1 k
~ ~
~ ~
n n
~ ~
~ ~
n n
~ ~
1 2

( )
3
3 2 2
, 3 2 1
) 4 (
1
~ ~ ~
, 48
2 1
1
3
2 1 k k k
k k k
k k
k k k k V P
k
e e e
e e e
+


( ) {
( )
1 3 3 1 2
2 1
1
1 3 3 2 2 1
k k k 2 k k k
2
3 k k k
2
3 k 2 k k
k k k k k k
n n n n n n 1 3
)
~ ~ ~
(
~ ~ ~
n n n n n n 1
+ +
e + e + e e
e + e + e
+ + +

e + e + e e
e + e + e
2
3 k k k
2
3 k 2 k k
)
~ ~ ~
(
~ ~ ~
2 1
1
(14.2)

And, phonon width is given as
( ) ( )
( ) ( ) | { |
1 1 2 1
2 1
2 1
2 1
~ ~
~ ~
) , , ( 9
Im
2
2 1
) 3 (
k k k k
k k
k k
k k
k k
n n
k k k V
P
e e e o
e e
e e
t
e e
+ + +
=
= I

( )
1 1
k k
~ ~
e e e o + (higher terms)
( ) ( ) ( ) | | }
( )
( ) {
4 3 3 2 2 1
3 2 1
3 2 1
3 2 1
2 1 2 1 1 2
k k k k k k
k k k
k k k 2
4 3 2 1
) 4 (
k k k
k k k k k k
n n n n n n 1 X
~ ~ ~
k , k , k , k V 48
~ ~ ~ ~
n n
+ + +
e e e
e e e
t +
e + e + e o e + e + e o +

( ) | | )
~ ~ ~
(
~ ~ ~
3 2 1 3 2 1
k k k k k k
X e e e e o e e e e o + + +

( ) ( )
4 3 3 2 2 1 4 3 3 2 2 1
k k k k k k k k k k k k
n n n n n n 3 n n n n n n 3 + + + +

( ) | |
)
`

+ + + )
~ ~ ~
(
~ ~ ~
3 2 1 3 2 1
k k k k k k
X e e e e o e e e e o (14.3)

) (
~
~
~ 2 2
T A
k k k
+ =e e , (14.4)

The Green' function (2) finally becomes
( )
( ) ( ) e e t
o
e
P
S
G
ij
x
i
ij
O
O
=
2 2
1

, (15)
February Issue Page 79 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

( ) e
p s
OA + O = O 2
~
~

2 2
, (16)
( ) e
s
OA + O = O 2
~
~
~
2 2
, (17)
| |
y
j
i
x
S F
S
1
1
2 2
,
1
4
~
O
+ O = O , (18)
In Eq.(18) second term is evaluated using mean field approximation i.e.

2
~
tanh
~
2
1
b
S
a
S
x
i 1
z
i 1 O
|
O
= =
(19)
which gives
bc b a + + = O
2 2 2
~
(20)
where
E S K S J a
z z
2 2
2 1
+ + =
(21)
O = 2 b ;
and
x x
S K S J c
2 1
2 + = (22)
Solving,Eq.(16)

x
i 1
2
ik
2
2 2
k
2 2
k
2
S V 8
~
~ ~
~
2
1 ~
~ ~
~
2
1

O + |
.
|

\
|
O e |
.
|

\
|
O + e = O

(23)
|
|
.
|

\
|
O
=

* J 4
tanh 2
2
3
1
q
q
B
c
k
T
(24)
where
( )
2 2 2 2 2
) 2 ( 4 2 E K J o q + O + = (25)
and
( )
| |
2 4
2 2
4
~
~
~
~
2
2 )* (
k k k
k ik
V
K J K J
I +
+ + = +
e e
e
(26)
J* is renormalized exchange interaction constant.

Hamiltonian of TGS crystal can be calculated by PLCM and Ising spin model with Greens function
theory of ferroelectrics extended with third and fourth order phonon anharmonic interaction terms and
electric field terms


( ) ( ) ( ) | |
( )


+
+ + O =
i
z
i
z
i
z
i
z
i ij
ij
z
i
z
i
z
i
z
i ij
i ij
x
i
x
i
S S E S S K
S S S S J S S H
) ( 2
2
2 1 2 1
2 2 2 1 2 1

|
.
|

\
| +
+
+
+
k
B
k
B
k
A
k
A
k
k
e
4
1

+


k
z
i ik
ik
k
z
i ik
ik
A S V A S V
2 1


February Issue Page 80 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

( )
3 2 1
3
,
2
,
1
3 2 1
) 3 (
k
A
k
A
k
A k k k
k k k
V +
( ) ,
4 3 2 1
4
,
3
,
2
,
1
4 3 2 1
) 4 (
k
A
k
A
k
A
k
A k k k k
k k k k
V +
(27)

Where, In Eq.(27) above O is proton tunneling frequency, S
z
and S
x
are components of pseudospin
variable J
ij
is interaction between same lattices and K
ij
is interaction between different lattices.

is
dipole moment of O-H--O bond, E is external electric field V is spin lattice interaction and A
k
and B
k

are position and momentum operators
k
e is harmonic phonon frequency V
(3)
and V
(4)
are third and
fourth order atomic force constant
15
.
The response of a dielectric crystal to the external electric field is expressed dielectric
susceptibility _ given as
( ) ( ) iX G N
ij X
+ =

e t e _
2 lim
0
2 (28)
The ( ) e _ is related to dielectric constant as
t_ 4 1+ e= (29)
With the help of Eq.(25) and (26) one obtain expression for dielectric constant as
( ) ( )
( )
(

I O + O
O
= e
2 2
2
2 2
1
2
4

8
e
t e
x
S
N
(30)
( ) e e >>1 in the ferroelectric crystal.
The power lost in dielectric when exposed to electromagnetic field is conveniently shown as dielectric
microwave absorption which is expressed as
e'
e' '
= o tan
(31)
By using Eq. (30) and (31) we obtains expression for loss tangent as
( )
( )
2 2

2
tan
O e
e OI
= o
(32)

We know that dielectric permittivity can be written as
c c c ' ' ' = i (33)
where c ' =real part of permittivity
c ' ' =imaginary part of permittivity
and magnitude of this complex number will be
) (
2
2
c c c ' ' + ' = (34)
and dielectric loss
e'
e' '
= o tan
(35)
Solve eq.(35) and eq.(36)
We have
)
tan 1
(
2
2
o
c
c
+
= '
and,
o
o c
c
2
2 2
tan 1
tan
+
= ' ' (36)
February Issue Page 81 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

2.1. Relaxation time

Relaxation time (minimum) is,
e
t
o
t
) tan
2
(
exp

=
(37)
2.2 Differentiability
tc
c
' '
2
= Function Smooth
(38)

3. Calculated theoretical results

In our calculation we use different theoretical values form literatures (Table1) and
substituted over PLCM and ISING spin models. Some literature values of TGS crystal are given
in table1.
Table 1. Different crystal constants

Crystal parameters Numerical values
Phase-transition temperature (Tc)
Curies temperature
Tunneling frequency ()
Angular frequency ()
Same lattices interactions (J)
Local field (V)
Position operator (A)
Dipole moment (N) (at 50
0
C)
Different lattices interactions (K)
Momentum operator (Bo)
322.25 (K)
3007 (K)
0.10 (cm
-1
)
0.59 (cm
-1
)
340 (cm
-1
)
10 (cm
-3/2
)
10.20
2.22 (C/cm
-2
)
0 (cm
-1
)
0

3.1 Theoretical results

After applying PLCM and Ising spin model for TGS crystal even in D.C. field which have a good
agreement with experimental results given below in figures 1, 2.



0.355
0.36
0.365
0.37
0.375
0.38
0.385
300 310 320 330 340 350
S
m
o
o
t
h

F
u
n
c
t
i
o
n

Temperature (K)
0 kv/cm
1 kv/cm
5 kv/cm
7 kv/cm
9 kv/cm
February Issue Page 82 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

Figure 1. Temperature denpendence of smooth function in presence of electric field for Triglycine
Sulphate Crystal -, Experimental values Dorogovtsev et al [13].



Figure 2. Temperature denpendence of minimum relaxation time () in presence of electric
field for Triglycine Sulphate Crystal -, Experimental values lsarek et al [14].

4. Discussion

This theoretical study about differentiability and minimum relaxation time (order of 10
-12
) of
triglycine sulphate (TGS) crystal shows very interesting results having a very balanced relation
with experimental data. We can say that triglycine sulphate (TGS) crystal has bistable
polarization which make it suitable for binary memory system with non-volatile and low
holding voltage features. To read the information by means of electric field of opposite polarity
have a wide range of possibility of application in computing memories. There is somewhat more
versatility in the recording mechanism. Its instance polarization reversible the memory can be
based on linear or quadratic electro-optics effects which arise from light-induced polarization
changes. Due to its tunneling mechanism it can be used in memory and display devices. This
crystal is helpful to store information in random or stable memories. Repeated fatigue c ycle
forced us to think about photo sensitivity and figure of merits of crystal and its isomorphs which
is satisfactory for optical memories and photo valves. Our dielectric permittivity is very high
(order of 10
3
) which is a direct symbol of high capacitive memories at quantum levels. Our
study also deal with the various properties of triglycine sulphate crystal which may make it
good raw material for display devices etc. here we have found that curie temperature (T
C
) of the
crystal slightly decreases with increasing order of field. Differentiability (smooth function of
order 10
-1
) have been studied by us which has highest value at curie temperature. It decreases
with increasing electric field. While we have got that relaxation time of the crystal has
minimum value at phase transition and it increases with increasing electric field. A best relation
between theoretical and experimental results [5, 6] shows that our study about TGS crystal is
best predictions about the crystal behavior and predictions about i ts application in computing
memories.

5. Conclusion

Our study about is much satisfactory and reliable to discuss about computing mechanism of
triglycine sulphate (TGS) crystal. It has also an important role in development of different
0.51
0.52
0.53
0.54
0.55
0.56
0.57
0.58
300 310 320 330 340 350

m
i
n

Temperature (K)
0 kv/cm
9 kv/cm
1 kv/cm
5 kv/cm
7 kv/cm
February Issue Page 83 of 84 ISSN 2229 5216
International Journal of Advances in Science and Technology

technologies like sensor technology, food technology and medical science. On the bases of these
properties we can say that PLCM (pseudospin lattice couple mode model) and Ising spin model
of ferroelectrics may applicable for other hydrogen bonded pyroelectric crystals like KDP
(KH
2
PO
4
) and Rochelle salt (NaKC
4
H
4
O
6
. 4H
2
O).


6. Acknowledgement

I am very thankful to Prof. P.K. Bajpai (Guru Ghasidas Univ. Chhatt.), Prof. S. Mollah
(A.M.U., Aligarh), Prof. S.K. Srivastava (Bundel. Univ., Jhansi)), Dr. Abhai Mansingh ( Delhi
Univ.) and Dr. V.R.K. Murthy (IIT Madras) for their kind advice.

7. References

[1] Mathias B T, Miller C E, Remeika, Phys. Rev.104,(1956) 449.
[2] Chaudhuri B K, Chaudhari K R and Banerjee S, Phys. Rev. B.38 (1988)689.
[3] Gonzalo J A, Phys. Rev. B1 (1970)3125.
[4] Zubarev D N,Sov. Phys. Usp.3,(1960)320-45.
[5] Dorogovtsev; S N and Yushin; N K,Ferroelectrics,112(1)(2011)27-44.
[6] lsarek; G, Idziak; S, Pilewski; N, and Stankowski; J,physic. Stat. solidi (b),110(1),(1982)233-
238.







Authors Profile



Prof. Trilok Chandra Upadhyay received his Ph.D degree from H.N.B.Garhwal
University, Uttarakhand, India in condensed matter physics. He is working on
ferroelectrics and condensed matter physics since more than twenty years and even
he has published more than eighty papers on ferroelectric material and condensed
matter physics. At present time, he is appointed as a professor in physics department,
H.N.B. Garhwal University, Uttarakhand, India.








Mr. Ashish Nautiyal born in uttarakashi, uttarakhand, india in 16 Oct1985. He has
completed his B.Sc. and M.Sc. (Physics) degree from birla campus, H.N.B. Garhwal
University, Srinagar garhwal, uttarakhad, india in 2005 and 2007 respectively. At
current time he is working on ferroelectric properties and applications of different
materials.



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