~ Solid S t a t e Communications, Vol. 46, No. 7, pp.

513-516, 1983
Printed in Great Britain.
0038-1098/83/190 513-04 $03.00/0
Pergamon P r e s s Ltd.

THE AsO~-CENTER IN CsH2As04: A HALPERIN-VARMA DEFECT MOVING IN A SINGLE WELL POTENTIAL

P.S.S. G u i m a r a e s , R. G a z z i n e l l i , G.M. R i b e i r o
and A.S. Chaves - D e p a r t m e n t o f P h y s i c s , ICEX,
U n i v e r s l d a d e F e d e r a l de Minas G e r a i s , C . P . 7 0 2 ,
Belo Horizonte, Brazil

(RECEIVED ON NOVEMBER 30th1982 by R.C.C. LEITE)

4-
The ESR o f t h e AsO 4 c e n t e r in CsH_AsO. is i n v e s t i g a t e d '
from 4.2K t o 270K. The b e h a v i o r o f th~s p ~ r a m a g n e t i c c e n t e r
is e s s e n t i a l l y different from i t s b e h a v i o r in t h e o t h e r
members o f t h e KDP f a m i l y . Two p r o p e r t i e s o f the c e n t e r a r e
r e m a r k a b l e : i t seems t o behave l l k e a H a l p e r i n - V a r m a kind of
d e f e c t and t o move c l a s s i c a l l y in a s i n g l e - w e l l potential
which can be r e p r e s e n t e d w i t h v e r y good a p p r o x i m a t i o n by
square w e l l .

The m i c r o s c o p i c model f o r the v e r s i (6) showed t h a t t h e a v a i l a b l e d a t a

f e r r o e l e c t r i c t r a n s i t i o n in hydrogen-bond
c r y s t a l s o f the KH2PO4 (KDP) f a m i l y has
been a m a t t e r of i n t e n s e i n v e s t i g a t i o n .
In h i s c l a s s i c a l paper S l a t e r ( l ) propo~
ed a mechanism based in the o r d e r i n g of
the hydrogens in a d o u b l e - w e l l p o t e n t i a l
along the l i n e c o n n e c t i n g the o x i g e n s of
n e i g h b o u r PO groups. The spontaneous
p o l a r i z a t i o n 4 o f KDP occurs along the
t e t r a g o n a l c - a x i s , whereas n e u t r o n -
d i f f r a c t i o n e x p e r i m e n t s by Bacon and
Pease (2) show t h a t the hydrogen motion
is almost e x a c t l y c o n t a i n e d in the ab-
plane. B a c o n and Pease a t t r i b u t e d the
p o l a r i z a t i o n o f the c r y s t a l t o the d i s -
placements of the potassium and phospho-
rus ions along the c - a x i s . The hidrogens,
however, should p l a y a c e n t r a l r o l e in
the t r a n s i t i o n mechanism in o r d e r to
e x p l a i n the pronounced dependence o f the
t r a n s i t i o n t e m p e r a t u r e T w i t h deuteration.
The c o n n e c t i o n between Cthese f a c t s was
c l a r i f i e d by Cochran ( 3 ) , who proposed
a s o f t mode f o r KDP made up by a correlated
motion o f the hydrogens and the heavy
ions: as the two protons in the upper
H-bonds o f a PO4 group move to s i t e s near
t h a t group, the two p r o t o n s in the lower
bonds move away, the P ions move down along the
the c - a x i s and the K ions move up along
t h i s same a x i s .
The e f f e c t o f d e u t e r a t i o n upon the
t r a n s i t i o n t e m p e r a t u r e was e x p l a i n e d by
Pirenne (4) and Blinc (5) as due to pure-
ly q u a n t u m - m e c h a n i c a l effects, on rather
distinct assumptions concerning the
s i n g l e - p a r t i c l e potential for the motion
of the protons (deuterons). Pirenne
postulated a single-well potential for
the bonds, whereas Blinc adopted the
double-well potential proposed by Slater.
The form of the potential for the bond is
still a matter of dispute. Silva and Ro-
on the v a r i a t i o n o f the s t a t i c p r o p e r t i e s
o f t h e c r y s t a l such as t h e i s o t o p i c depen
dence o f t he t r a n s i t i o n t e m p e r a t u r e , Curie
c o n s t a n t and s a t u r a t i o n p o l a r i z a t i o n ,
c a n n o t d i s c r i m i n a t e between the s q u a r e -
well potential initially e x p l o i t e d by
P i r e n n e and the d o u b l e - w e l l t u n n e l l i n g
bond proposed by B l i n c . E m p i r i c a l models
f o r the h y d r o g e n - b o n d p o t e n t i a l were
r e c e n t l y p r o p o s e d and i n v e s t i g a t e d by
Lawrence and R o b e r t s o n (7) and by Inoue
and S h i r a i s h i (8).
Many i n v e s t i g a t i o n s have been done
by ESR on the KDP f a m i l y u s i n g paramagne-
t i c c e n t e r s at the s i t e o f t h e P i o n . Such
i n v e s t i g a t i o n s were s t r o n g l y m o t i v a t e d by
t h e ESR s t uL d y by B l i n c , Cevc and Schara(9)
on the AsO~- c e n t e r in KH_AsO. (KDA),whe
re the spedtraU c a r a c t e r i s ~ i c ~f the
f e r r o e l e c t r i c phase were found to remain
in the p a r a e l e c t r l c phase up to a tempe-
r a t u r e T* c o n s i d e r a b l y h i g h e r than T .
Reviews o f the s u b j e c t were made by c
Adriaenssens (10) , Dalal ( I l l and others.
The a u t h o r s o f those i n v e s t i g a t i o n s
reached the unanimous c o n c l u s i o n t h a t
the anomaly is due to the o c c u r r e n c e , in
the p a r a e l e c t r i c phase, o f p o l a r i z e d
c l u s t e r s which are l o n g - l i v e d in comparison
w i t h the time scale of the soft-mode dyna
mics. This l o w - f r e q u e n c y dynamics o f t h e
o r d e r parameter was a l s o found to occur
in many o t h e r s t r u c t u r a l phase t r a n s i -
t i o n s by i n v e s t i g a t i o n s using a g r e a t
v a r i e t y of e x p e r i m e n t a l techniques and
the phenomenon is denominated c e n t r a l
peak (CP). Most Of the observed CP are
now recognized t o be not i n t r i n s i c to
p h a s e - t r a n s l t l o n dynamics, but caused by
d e f e c t s o f the c r y s t a l . In p a r t i c u l a r ,
the accumulated e v i d e n c e support the
c o n c l u s i o n t h a t a l l the CP observed by
ESR e x p e r i m e n t s are a f f e c t e d by the

513
 514 THE AsO ~ - ~ N T E R IN CsH2AsO 4 Vol. 46, No. 7
p a r a m a g n e t i c probe - a p o i n t d e f e c t on Th~ ESR s p i n H a m i l t o n i a n describing
the system under s t u d y . Two a l t e r n a t i v e t h e AsO~- c e n t e r i s g i v e n by
models a r e a v a i l a b l e f o r p o i n t - d e f e c t 4+
induced CP. H a l p e r i n and Varma ( 1 2 ) , in H = ~ . g...S. . . + ? . ~ . ~ + ~ i .~.~, (i)
an i n d e p e n d e n t w o r k , d e v e l o p e d in d e t a i l P P
a model f i r s t proposed by Burns ( 1 3 ) . p=l
Such model, g e n e r a l l y known as H a l p e r i n - where S = 1 / 2 , ] = 3 / 2 , 1 = I / 2 , a n d A and A
Varma (HV) model, p o s t u l a t e s t h a t the p P
are the hyperfine interaction tensors
d e f e c t has an i n t r i n s i c dynamics which
breaks the l o c a l symmetry o f the system for the arsenic and t h e f o u r p r o t o n s
in the same way as the o r d e r p a r a m e t e r , s u r r o u n d i n g t h e radlca]. The g r o s s f e a t u
r e s o f t h e ESR s p e c t r a are dominated by-
and c o n s e q u e n t l y i t s dynamics w i l l c o u p l e
t h e l a r g e v a l u e o f A, w h i c h g i v e s o r i g i n
l i n e a r l y w i t h t h e s o f t mode, i . e . , the
to a large splitting of the I quartet.
intrinsic dynamics o f t h e o r d e r p a r a m e t e r .
Each l i n e o f t h i s quartet shows a p o o r l y
That c o u p l i n g r e n d e r s a c r i t i c a l behavior
t o t h e d e f e c t dynamics w i t h the s o f t mode r e s o l v e d s t r u c t u r e w h i c h h a v e b e e n shown
is t o o weak t o a f f e c t a p p r e c i a b l y t h a t (9,16,19) to result from the protons hy-
perfine interactions and f r o m t h e
d y n a m i c s . I n a v a r i a t i o n of the HV model the
different orientations of the "g- tensor,
coupling of the defect dynamics with the soft corresponding to opposite ferroelectric
mode is too weak to affect appreciably that dy- domains, each one containing two chemi-
namics. Thus, the defect dynamics is not c r i t i - cally-equi~alent but magnetically-unequ~
cal, i . e . , doesn o t follow the showing-down of valent As04- sites. This structure is
the so'ft-mode near the c r i t i c a l temperature,but
i n s t e a d f o l l o w s the A r r h e n i u s law f o r better resolved for the lowest-field
t h e r m a l l y a c t i v a t e d processes ( ] 4 ) . In (MI= 3/2) line of the quartet, and thus
the second model, proposed by H~Ick and we c o n c e n t r a t e d most of our a t t e n t i o n to
T h o m a s (15) (HT), the defect does not the study of this line. Figure I shows
b r e a k the local s y m m e t r y of the system, the a n g u l a r v a r i a t i o n of the M.= 3/2 and
but c h a n g e s locally the p a r a m e t e r s of the M = -3/2 lines, taken at 90K i~ the
many-particle Hamiltonian which describes f ~ r r o e l e c t r i c phase. The centers of the
the phase t r a n s i t i o n and, in p a r t i c u l a r , lines are isotropic in the a b - p l a n e . The
the s o f t - m o d e behavior. Under certain fa w h o l e s p e c t r u m shows no s i g n i f i c a n t
v o r a b l e c o n d i t i o n s the r e s u l t i n g effect changes from 4K to 270K, where the
is the increase in the t e m p e r a t u r e at p a r a m a g n e t i c center b e c o m e s unstable.
w h i c h one o b s e r v e s the local s y m m e t r y - The values of +9 and A o b t a i n e d from
b r e a k i n g a r o u n d the defect. Though all the m e a s u r e m e n t s in figure l are in
three v a r i e t i e s of CP have been claimed to be r e s o n a b l e a g r e e m e n t wit~ those p r e v i o u s -
observed, it might be that all the CP observed by ly o b t a i n e d by Dalai et. al (19). Howe-
ESR in. the KDP family reported in the literature can ver, the s t r u c t u r e o b s e r v e d in the Ml=
be u n d e r s t o o d w i t h i n the f r a m e w o r k of 3/2 t r a n s i t i o n is quite d i s t i n c t from
the HT model (16,17). that o b s e r v e d by Daia] et al. in CDA and
The crystal C s H _ A s O ~ ( C D A ) is from the reported results in all the
i s o m o r p h o u s with KDPZand 4 has a similar other m e m b e r s of the KDP family. Our
t r a n s i t i o n from a tetragonal (l~-2d) results are u n c o n s i ~ t e n t with the hypo-
p a r a e l e c t r i c phase to an o r t h o r h o m b i c thesis that the AsO~- center p r e s e r v e s
(Fdd2) f e r r o e l e c t r i c phase at T = I 4 0 K the s y m m e t r y of the AsO~- site. If this
(18). T h i s 4 P a p e r reports an ESR = study symmetry were p r e s e r v e d ; each member of
of the A s O ~ - c e n t e r in IDA which shows the As quartet should split, in the
s i g n i f i c a n t d i s t i n c t i o n s from the simi- f e r r o e l e c t r i c phase, in two lines for
lar studies found in the l i t e r a t u r e for ~ m a q n e t i c field in the d i r e c t i o n
other a r s e n i d e m e m b e r s of the KDP family, = a ÷ + +~ (17). However, as it can be
and for CDA itself (19). The samples, seen in figure 2, for that o r i e n t a t i o n
o b t a i n e d from General Diode C o r p o r a t i o n , of the field we have at least three
were i r r a d i a t e d at 77K with, X-ray for lines. In fact, by c o m p u t e r fitting the
the p r o d u c t i o n of the AsO~- center. The l i n e s h a p e we could see that there are
~t
i r r a d i a t e d s a m p l e s were t r a n s f e r r e d to four lines in figure 2, the line in the
an ESR s p e c t r o m e t e r at low t e m p e r a t u r e middle being an u n r e s o l v e d doublet. The
in order, to p r e v e n t the d e s t r u c t i o n of p r e c i s i o n of the sample o r i e n t a t i o n in
the A s O ~ - c e n t e r , w h i c h d e c a y s very the m a g n e t i c field (10) is high e n o u g h
q u i c k l y - a t t e m p e r a t u r e s h i g h e r than about to rule but m i s a l i q u e m e n t as a reason
270K. Two p a r a m a g n e t i c centers, A s O 4 - a n d for the a p p r a r a n c e of more than two lines
AsO 2-, are c r e a t e d by i r r a d l a t i o n ( l ~ ) , a s in figure 2. The s p e c t r u m for H//C is
usual for the a r s e n i d e m e m b e r s of the also quite amazing. Instead of a triplet
KDP family, but the A s O ~-T- c e n t e r has which transforms into a quintet (9) at
r e c e i v e d much more a t t e n t i o n in the lite some t e m p e r a t u r e T* > Tc, t h e spectrum
rature due to its a b i l i t y to m a n i f e s t CP- shown in f i g u r e 3 was o b s e r v e d . That
p h e n o m e n a . This c e n t e r is formed by the spectrum shows no change when t h e tempe-
traI~ping of one extra e l e c t r o n by the r a t u r e is changed from 4K up t o 270K. The
AsO~- radical and a c c o r d i n g to the l i n e s h a p e o b s e r v e d in f i g u r e 3 cannot be
p r e ~ e n t e v i d e n c e s (17,19), the local f i t t e d by a q u i n t e t o r a t r i p l e t . In
s y m m e t r y of this radical is p r e s e r v e d f a c t , t h a t spectrum can be reproduced
after the c a p t u r e of the extra e l e c t r o n . o n l y by the sum o f a v e r y l a r g e number o f
 515
Vol. 46, No. 7 THE AsO~-CENTER IN CsH2AsO 4

j ~ T9
,0K
4700
0/0
Gauss

4650
/
I

/
4600
/ Figure 2 - The s t r u c t u r e of the lowest

4550
/ field (M, = 3/2) line, at T = 90K and
= 904~IMH~,
along
fgr the m a g n e t i c field
X = a + b.

T=90K

4500

I 450
Lo 1450G
I 400 3 - The s t r u c t u r e of the lowest
field (M, = 3/2) line, at T = 197K and
v = 9 0 0 5 1 M H z , for the m a g n e t i c field
along c. The n o i s e l e s s line r e p r e s e n t s
the best fit with formula 5 of the text.
I 35C and r e s o n a n c e m a g n e t i c field H R for that
value of the c o o r d i n a t e s is
2
HR ~ Ho + h l z + h2z (4)

,5oo
0
, 30 ° 60 =
:~;""'~ C
The best c o m p u t e r f i t t i n g s of the
l i n e s h a p e were o b t a i n e d with very s h a l l o w
double-well p o t e n t i a l s and with hi>> h 2.
Figure I - Angular variation of the An even better f i t t i n g was o b t a i n e d by
lowest-(M1=3/2) and highest field a d o p t i n g the s q u a r e - w e l l potential and
(M,=-3/2) lines a t T = 90K a n d v = 9 0 4 2 by making h 2 = 0. The s i n g l e - l i n e w h i c h
MH~. E a c h l i n e of the l = 3/2 quartet is gives the best fitting has a Gaussian
a poorly resolved structure and the lineshape, and thus the t h e o r e t i c a l
fields shown in the figure are taken at l i n e s h a p e is
the center of the structure. The c e n t e r
of the structure is isotropic in the
ab-plane. The s p i n - H a m i l t o n i n a n parame- H + H
ter obtained from the data are I(H) d Hd fH ° - HI e x p l . 0 . 6 9 3 ( H _ H R ) 2 / y 2 1 d H R
gx = gy = gz = 2 . 0 0 0 + 0 . 0 0 5 , A = A o I
= (2757 + 10) MHz, Az (3091 +- xlO) MHz.Y
(5)
The comparison b e t w e e n t h e f u n c t i o n I
Iines and s u g g e s t s that the s y s t e m h== a (H) a n d e x p e r i m e n t is seen in figure 3.
c o n t i n u o u s d i s o r d e r . Trials for explaining The fitting parameters were H = 1286
thespectrum were made s u p p o s i n g that the Gauss, H 1 = 55,6 Gauss and y ~ 15,5 Gauss.
AsO~-moves classically in a double well Some ramarks should be made about
potential of the form these results. From e q u a t i o n (4) and the
fitting p a r a m e t e r s (h1>>h2), one sees
V(z) = -az 2 + bz 4, a,b > 0, (2) that the resonance field can discrimina-
w h e r e z is p r o p o r t i o n a l to the local
p o l a r i z a t i o n . The p r o b a b i l i t y of finding
the c e n t e r at a c e r t a i n c o o r d i n a t e z is
te polarization
i.e.,the
spontaneously
paramagnetlc
up and p o l a r i z a t i o n
center
the symmetry of the AsO~-
breaks
down,
?
site and the resulting perturbation
p(z) = Ce- V ( z ) / k T , (3) which i t c a u s e s on t h e s y s t e m c o n t a i n s
 516 AsO~-CENTER~ IN CsH2AsO4 Vol. 46, No. 7

the i r r e d u c i b l e r e p r e s e n t a t i o n B2 o f the Furthermore, the As0~-defect does not

order parameter for the ferroelec~ric
transition. O t h e r w i s e , H (z) s h o u l d
c o n t a i n o n l y even powersRof z. T h i s is
c o n s i s t e n t w i t h t h e a p p e a r a n c e o f more
than two l l n e s in t h e X d i r e c t i o n , as
d i s c u s s e d b e f o r e and shown in f i g u r e 2.
The symmetry b r e a k i n g , e v i d e n t i a t e d by
the a p p e a r a n c e o f a l i n e a r t e r m in the
e x p a n s i o n o f H(z) and by th e e x i s t e n c e o f
f o u r l i n e s f o r the magnetic f i e , l d along
the X d i r e c t i o n , s u g g e s t s t h a t the AsO~-
probe behaves l i k e a H a l p e r i n Varma
defect.
move in a double w e l l p o t e n t i a l , but in a
s h a l l o w s i n g l e w e l l p o t e n t i a l which can
be described w i t h every good a p p r o x i m a t i o n
by a square w e l l p o t e n t i a l . E v i d e n t l y , o n e
should be aware of the f a c t t h a t the
p o t e n t i a l f o r the motion of the d e f e c t i v e
group can be q u i t e d i f f e r e n t from the
p o t e n t i a l f o r the motion of the
s u b s t i t u t e d AsO~- radical.
We thank Dr. Ivone Mascarenhas f o r
e s t a b l i s h i n g the c r y s t a l o r i e n t a t i o n by
X-ray. This work was supported by FINEP,
CNPq and CNEN.

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