58 2 S tn tc tu r e u n d s c a tte r in g

2 7 L iq u id c r y s ta ls

W e ha ve lo o ke d a t tw o e x tr e m e ĺ o rm s o f co n de n se d m a tte r : ho m o ge n e o L ıs
,

is o tr o p ic liq u id s w ith a n a v e ra ge s tr u c tu r e t h a t is in v a r ia n t u n de r a r b it r a r y

r o ta tio n s a n d t r a n s la tio n s a n d c r y s ta llin e so lid s w ith a v e ra ge s tr u c tu re s th a t

,

a re in v a r ia n t o n ly w it h re s p e c t to c e f ta in d is c r e te la tt ic e t r a n s la tio n s a n d p o in t

g ro u p o pe ra tio n s c o m p r is in g th e s p a c e gro u p T h e liq u id s ta te h a s s h o r t r a n g e

o rd e r i) u t n o lo n g ra n ge o rd e r : it h a s th e h ig h e s t p o s s ib le s y m m e t r y T he
c r y s ta llin e so lid s ta te ha s lo n g ra ng e p o s itio n a l a n d r o ta tio n a l o r d e r ; ir h a s a

m u c h lo w er sym m e tr y th a n th e liq u id s ta te a n d ca n ha ve th e lo w e st po s s ib ı
e

sym m e tr y c o n s is te tıt w ith a g u la r fillin g

re o f sp a ce B e tw een th e s e ex tr e rn e s

th e r e a re s y s te m s th a t e x h ib it s h o r t r a n g e c o r r e la tio n s in so m e d ir e c tio n s an d
lo n g r a n g e o r d e r in o t h e r s a d th a t h a v e s y m m e t r ie s in te r m e d ia te b e tw een th o s e
o f liq u id s a n d th e c r y s ta ls O n e fo rm o f th is in te r m e d ia te o r d e r is o r ie n t a tio n a l
o rd e r In a p e r io d ic c r y s ta l, th e r e is o n ly a d is c r e te se t o f d ir e c tio n s d e tin e d
by v e c to r s b e tw een n e a re s t n e ig h b o r p a r t ic le s w h ic h o cc u p y s ite s o n a la ttic e
,

T h e s e d ir e c t io n s a re th e sa m e th r o u gho u t th e la ttic e a n d d e fin e a lo g ra n

n ge
o r ie n ta t io l o rd e r o fte n lle d b o d
n a c a n g le
a ïı o rd e r R e m a rk a b ly it is p o s s ib le to
,

ha v e lo n g ra n g e o r ie n ta tio n a l o r d e r in th e a b se n ce o f tr a n s la tio n a l o r d e r

A o n g th e m a te r ia ls t h a t s h o w in te r m e d ia te o r d e r th e m
m o st w id e ly s tu d ie d a re
,

liq u id c r y s ta ls S o m e e x a m p le s o f liq u id c r y s ta l fo r m in le c u le s sho w n in

g m o a re
F ig 2 7 1 T h e m o le c u le s a r e h ig h ly a n is o t r o p ic a n d to a o d
g , o a p p r o x im a tio n c a n
be d e le d a s r ig id ds llip s o icis f lu tio ith le g th s
m o ro o r e o re v o n w n g r e a te r t h a n
th e ir w id th s a s sho w n in F ig 2 7 2 A is t h e ith lid s th e o r ie n ta
a s c a se w so ,
tio n a l
o r te r is ca u se d m o s tly b y th e re p u ls iv e in te r a c tio n s t

A t h ig h te m p e r a tu re s th e a x e s o f th e a n is o tr o p ic m le c u le s
o a re r a n do m ly o r ie n te d
a n d th e ir c e n te r s f m a ss a re ra n do ly d is t r ib u te d
a s d e p ic te d in F ig
m ů
2 7 3a
G lo b a lly th e a n is o t r o p jc liq u id
s y s te m is
T h e s tr u c tu r e fa c to r (F i 2 7 4 a ) is
g
is o t r o p ic b u t s h o w s liq u id lik e r in s a t w a v e n b
g u m e r s c o r r e s p o n d in
g to th e tw o
c h a r a c te r is tic le n g th s o f th e in d iv id u a l
m o le c u le s th e ir le n g th 1 a n d d ia m e te r Ĺı

t T he n am es o r th e d ifle r e n t liq u id c r s t a lı
y in e p h a s e s a r e d u e 1o ( i F r ie d l h
e w o s tu d ie d m a n y o f
th e ir p r o p e r tie s in t h c ń r s t p a r t o f th e tw e n tie th c e n tu r N i i f th e G r e e k v Iı
th re a d W h e n o b s e r v e d b e tw e e n c r o s d
y e m a t c s ro m /ıG tb r
se po ı a r iz e r s th e d e fe c ts i
n lłe m a tic s p r o d u c e a th r e a d lik e
s tr u c tu r e S m e c tic s a r e fr o m
za lb r s o a
(T Il t / ı
p fr o m w h ic h m a n y ı a y e r e d m e s o p h a s e s a re m a d e
C h o le s te r y l n o n a n o a te w a s t h e ĥ r s t li i
q u d c r y s ta l d is c o v e r e d b
R
y R e in itz e r a n d 0 L e h m a n (in
th e la te n in e te e n t h c e n tu r
y ) a n d g iv e s its n a m e to c h o ł e s te r ic s L o tr o
w h ic h u n d e r o
y p ic r e fe r s to liq u id crs[als
g p h a s e c h a n g e s a s a fu n c t io n o f s o lv e n t
c o n c e n tr a tio n w h ile Ŋh e r m o t r u
w ith te m p e r a tu r e a s a c o n t p ic s c h a n g e
m l p a r a m e te r T h e n a
m es s m e c l ic A s m e c t ic C
"
t
e c M e r e ly
in d ic a te t h e h is to r ic a l o r d e r i
n w h ic h t h e
p h a s e s w e r e d is c o y e r e d T h e r e is n o t t h e s li ı
a b o u t th e a r r a n g t te s t c lu e
g e n ie n t o ĺ t h e m o le c u le s th e s m
y m e lr ie s o r th e p h y s ic a l r o e r t ie s in th e ı e tte r
d e s ig n a t io n IG F r ie d e l
A n ıı P h y s i u e ( P u r is ) ı8
p p
q 2 7 3 ( 1 9 2 2 ) F R e in itz e r W n ıu t s Ĺ II C /]e m 9
4 2 1 ( 1 9 8 8 ); 0 L e h m l
a n Z P lły s ik a ıg IlL n ı 4 + 6 2
, \ ıŲ 8 Ų ) 1

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 27 L iq u id c r y s ta ls

59
4 ,4 d im e t h y lo y be
x y a zo x m en e (az o xy a ni s ol e )

H gC O N

Ţ O C Ha

1 18 2 C 13 5 3 C
so lid < N I
29 57k 1 0 67kJ

2 (4 n p e n ty lp h e n y l) 5 (4
- 7c Į »e n t y lo x y p h e n y l) p y r in i
ı d in e

C óH 1 10
C oH n

"
so lid . . Sm G ° L °7

Sm F
" 8
L Sm C į
44C
S rn A I
34 98kJ . .
0 58 k J 0 5kJ 11 45kJ 0 2kJ

4 n p e n t y lb e th io 4 h e p t y lo x y b e đ
đ en e n o a te (T S 5 )

C 7H 1ö o
lj
S C óH 11

37C 8 1C

F IF 2 7 1 S o m e m o le c itle s fo r m in g liq u id c r y s ta l p h a s e s a n d th e ir p h a s e
se q u e n c e s a s a fu n c tio n f te m p e r a tu r e T h e b e n z e n e ń n
m o le c u le s
o
gs g iv e ń g id ity to th e

W he n th e is o tr o ic
p liq u id is c o o le d th e fir s t h a s e th a t c o n d e n s e s i th
p , s e
n em a tic (N ) p h a s e in w h ic h lo n m o le c l
g li
u e s a g n s o th a t th e y a r e o n a v e r a e
g
p a r a lle l to a p a r tic u ı a r d ir e c tio n s e c ifie d b
T h e p o s itio n s
p y a u n it v e c to r n c a lı e d th e d ir e c to r
o f th e m o le c l
u a r c e n te r s o f m a s s r e m a in r a n d o m l d is tr ib u te d a s
th e y a r e in y
a n is o tr o ic fl
p u id T h e n e m a tic p h a s e b r e a k s r o ta tio n a l is o tr o p y b u t
n o t tr a n s la ti
o n a l in v a r i
a n ce R o ta tio n s a b o u t a n a x is p a r a lle l to n le a v e th e
n e m a tic
p h a se u n c h a n e d w h r
g , e e a s r o ta tio n s a b o u t a x e s p e r p e n d ic u la r to ı ıd o
n o t T he
n e m a tic
p h a s e s till h a s a n a x ia l r o ta tio n a l s y m m e tr
is r e g a r d e d y If e a c h m o le c u le
a s a r i id r d
g o w h o s e lo n g a x is m a k e s a n a n le O w ith r e s p e c t to
th e n a g
m e a s u re f th e d e r e e o f o r d e r in th e n e m a tic
p h a s e is p r o v id e d b y
o
s = (c o s 2 e 吕
į
> n s a g e r (1 9 4 9 ) h a s s h o w n th a t th e tr a n s itio n fr o m th e is o tr o p ic
o

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r
센
拙

7 s 5 (F ig 2 7 1 ) (b ) M o d e l
F ig 2 7 2 (a ) S p a c e fillin g m o d e l fo r t h e m o le c u le
id o f re v o lu t io n w ith le n g t h 1 a n d d ia m e te
r a
o f (a ) a s a r ig id r o d o r e llip s o

f th e m o le c u le s
to th e n e m pha
a tic se is p r e d o m in a n tly a r e s u lt o f th e s h a p e o
i r o p ic h a r d c o r e r e p u ls io n )
H is c a lc u la tio n p r e c e d e d
a n d ex c lu d e d v o lu m e ( a n s o t ,

s o lid B a s ic a lly
t h e s im u la tio n s o r t e
h t r a n s itio n o f h a r d s p h e r e s fr o m liq u id to
li n in g th e ir
h p a c k ın g d e n s ity o r m a tc h s tic k s b y a g
it is e a s ie r to a c h ie v e a h ig d m ly
n d ir e c tio n r a th e r th d n b y a o
ll w in g th e m to b e r a n o
a xes a lo n g a c o m m o
i b y w a y o f a n in c f e a
se
h i id t i n e n te r s th e th e r m o d y n a m c s
o r ie n te d ( T s c o n s e r a o
tic p h a s e
T h e s t r u c t u r e fa c to r o f th e n e m a
in e n tr o p y fo r t h e a lig n e d s ta e )
t
la n e
h b k i n g o f r o ta tio n a l s y m m e tr y
It is a x ia lly s y m m e tr ic in a ir y p
re fl e c t s t e r e a

l t w o fo ld s y m m e tr y in a n y p a n
l e c o n ta in in g n
d ic u l a r t o n b u t h a s o n y
p e rpe n r o ic
h r t d is ta n c e ) s p h e r e
o f th e is o t p
T h e in te n s ty o i f t h e l a r g e w a v e n u m b e r ( s o
s it
i d t o w a r d th e p la n e p e r p e n d c u a r
i l to n w h e r e a s th e in te n y
h s c o m p re s se
s ib le
p a s e
b h e r e is c o m p r e s s e d to w a r d t e
h n a x is T w o p o s
o f th e s m a ll w a v e n u m e r s p 4b
h a t ic p h a s e a r e s h o w n
in F ig s 2 7
h x i t e n s i t y f r o m t e n e m
fo r m s fo r t e f a y n
he
d if r t t w ith ą o
- 2 n /1 a n d in t
a n d c In th e fir s t t h e r e a r e u s e s p o s a
=
q ą o n ,

d ifĮ u s e r in g s c e n t e r e d a t th e s a m e v a lu e s o f q
s e c o n d th e r e a r e
in F ig 2 7 5 a )
a re
h h l r o l n o n a n o a te s h o w n
E h ir a ı m o e c u l l e s ( s u c a s c o e s t e
tic
a nem a
i l W h e n s u c h m o le c u le s a f e a d d e d to
m o le c u le s w it h n
o m rro f p a n e
fte n
) s ta te r e s u lts T h is s ta te is o
Ĺ /ıir a t n e n ta t ic (N
'

liq u id c r y t l a t w is t e d o r
s a ,
v e r a g e n ro
le c u la r
h h l t i s t a t e I n t h i s s ta te th e d ir e c tio n o f a
r e k r r e d to a s t e c o e s e r c ,
i ta n c e
li l t s h o w n in F ig 2 7 5
b T h e p itc h (d s
a lig n m e n t r o ta te s
in a h e c a p a t e r n a s

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 27 L iq u id c r y s ta ls
61

b e tw e e n e q u iv a le n t p la n e s ) d e p e n d s o n th e c o n c e n tr ti
a o n a n d de
g r e e o f c h ir a lity
o f t h e c h ir a l m o le c u le s b u t is ty p ic a lly o f o r d e r
s e v e r a l th o u s
a n d a n 8 s tr o n ıs T h i
s
M e a n s t h a t c h o le s te r ic s B r a g g s c a tte r v is ib le li h t
g T h e ir X r a sc a tte r i
y i
n g n te n s it
y
is , h o w e v e r , g e n e r a lly s iln iıa r to th a t o f a n
e m a tic

2 Sm e e tie s A a n d C

Ą s te m p e r a tu r e is fu r th e r re d u c e d, m o le c u le s b e g in to se g r e g a te in to p la n es g iv in g
ń se to a sm e c tic A (S m A ) liq u id c r y s ta l T he u su a l p ic tu r e f th is
s m e c tic p h a s e is o
o n e w ith m o le c u le s s itu a te d in
ll d e fin e d la e r s w ith w e
y a s p a c in g t h a t is e s s e n tia ll
t h e r o d le n g th a s s h o w n in F i 2 7 3 c T
y
g h e r e is liq u id lik e m o tio n o f th
e r o d s in
e a c h la y e r a n d n o c o r r e la tio n o f t h e
p o s itio n s o f th e m o le c u le s fr o m o n e la e r to
y
t h e n e x t In s m e c tic A ı iq u id c r y s ta ı
s m o le c u le s a r e a li n d
g e p e r p e n d ic u la r to th e
,

la y e r s T h e in t r o d u c tio n o f t h e la e r in i d i
y g n c a te s th e p r e s e n c e o f a m a s s d e n s ity
w a v e p e r p e n d ic u la r to th e la e r s T h e r e is th e r e fo r e
y , p o s itio n a l c o r r e la tio n in ,

th e s y s te m w h ic h c a n b e d e s c r ib e d a s a s in u
s o id a l m o d u la tio n o f th e a v e r a e
g
m o le c u la r numberensity
,

<n (x )> = no + 2 n qo co s (q o z ) , (2 7 1 )
w h e r e ąo 2 7【/1 a n d th e
-
z a x is is a lo n g th e la y e r n o rm a is a n d p a r a lle l to n T he
F o u r ie r tr a n s fo r m o f th is e q u a t io n le a d s to tw o B ks a w a y fr o m O in
ra gs p e a q =

t h e s tr u c tu r e fu n c tio n

2 3
S (q ) - fn q >ı (2 n ) [ô {q
. z ąo e , ) + ò (q , + ąo e , )] (2 7 2)

W e sh a ll s e e in C h a p te r 6 th a t th e r m a l flu c tu a tio d e s tr o y th e id e a l lo n g r a n g e
n s

p e r io d ic o r d e r o f th e s m ec tic p h a s e a n d th a t th e r e a r e p o w e r la w s in g u la ń tie s
r a th e r th a n d e lt a fu n c tio n sp ik e s in S (q ) at q = 土q o e z Thu th e p e a k s in th e

sm ec tic s tr u c tu r e fu n c tio n a re ca lle d q u a si B ra gg ra th e r th a n B ra gg peak a n d

sm ec tic s a r e th u s sa id to be c ha r a c te r iz e d b y q u a s i lo n g r a n g e o r d e r (Q L R O )

ra th e r th a n tr u e lo n g ra n ge o rde r (L Ŕ O ) A s th e s m e c tic p h a s e is a p p ro a ched o n

co o lin g fr o m th e n em tic p h a s e , th e d iflu s e s p o ts (F ig 2 7 4 b ) in th e n e n ıa tic

a
h s i B r a g g p e a k s o f th e
s tr u c tu r e fa c to r s h a r p e n a n d e v e n tu a lly b e c o m e t e q u a
i
s m e c tic p ha se A n e x p e r im e n ta l in te n s ity p r o file o f th e se p e a k s is s h o w n n
F į g 2 7 6 T h e tr a n s itio n fr o m th e n e m a tic to th e s m e c tic A p h a s e c a n b e s e c o n d
in g c o n tin u o u s ly fr o m z e r o a s w e
o r d e r w ith th e m a s s d e n s it
y a m p litu d e g r o w
w ill s e e in m o r e d e ta il in C h a p te r 4 T h e e x p e r im e n ta l s tr u c tu r e fa c to r o f m o s t
th e r m o tr o ic s m e c tic s h a s o n ly tw o q u a s i B r a g g p e a k s (a t t q o ) n
i d ic a tin g th a t
p
th e s in g le s in e w a v e in E o o d r e p r e s e n ta tio n o
f t h e a c tu a l d e n s ity
q (2 ? 1 ) is a g
o n e n ts
in th e s m e c tic in c o n t r a s t to th e s q u a r e w a v e w ith m a n y F o u r ie r c o m p
im p lie d b th e u s u a l s c h e m a tic r e p r e s e n ta tio n (F ig 2 7 3 c )
ı

y
l ti to th e s m e c tic
In s o m e s y s te m s m o le c u le s a lig n a lo n g a n a x is tilte d r e a v e
It h a s a lo w e r
,

p la n e s a s s h o w n in F ig 2 7 3 d T h is is th e s m e c tic C p h a s e
il d m o le c u le s p ic k o u t a
e b e c a u s e th e t te
y th a n t h e s m e c tic A p h a s
s y m m e tr
la n e a lig n
e c tio n s in th e x y p
i th e s m e c tic p la n e i e , th e ir p r o j
,
s p e c ia l d ir e c ti o n n ,

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 w
ı « ow ðC « tte r ı
n g

(a )

F ig 2 7 3 S c h e
m a tic r e r e s e n t ti
p a o n o f th e
p o s itio n a n d o r ie n ta tio n o f
a n is o tr o ic m o l
p e c u le s in (a
) th e is o tr o p ic , (b ) th e n e m a tic (c ) th e s m e c tic A
a n d (d ) th e s m
e c tic C
p h a s e s T h e d ir e c tio n o f a v e r a e
, ,

in a ll b u t th e is o tr g m o ie c u la r a lig m n e n t
o p ic p h a s e is s
in th e s m e c tic h p æ ilie d b y a u n it v e c to r n T h e la y e r n o m ıa l
p a s e s is in d ic a te d b th
y e u n it v e c to r N In th e sm e c tic A
P h u ie n is p a r a lle l to N
,
w h e r e a s in th
N = e . Is a r a lle l , e s m e c tic c p h a s e it is n o t In th e te x t
p to t h e z a x is ,

m o le c u le s in th
( ) a n d (d ) a ls o s h o w th e a r r a n g e m e n t o f
c
e s m e c tic
p la n e s in th e s n ie c tic A ą n d c
sn ı æ tic C p h a s e th p h a s e s In th e
, e p r o je c tio n s o f m o le c u la r
P e \ n d ic u la r to N a ı a x e s o n to th e p la n e
is n o n a v e r a
g e a lo n g th e c d ir e c to r

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27 L iq u id c r y s ta ls
63

(E )
»

・ ・

ąo

\
\ /

lķ 4r

(e ) (f)

F ig 2 7 4 S c h e m a tic re p re se n y s c a tte r in g in te n s itie s p r o ó le s

ta tio n o f X ra
fr o m (a ) th e is o tr o i
p ç (b ) a n d (c ) th e n e m a tic (d ) th e s m e c tic A a n (e ) a n
, ,
d d
,

(f) th e s m e c tic c p h a s e s A ll in te n s itie s p r o file s a re c r o s s se c tio n s in a p a n e l

c o n ta in in
g th e d ir e c to r n T h e fu ll th r e e d im e n s io n a l p r o file s fo r (a ) th r o u g h
( ) a r e o b ta in e d b y r o ta tin g th e c r o s s s e c tio n a l p r o file s a b o u t ıı (b ) a n d (c )
d
a ppl
y r e s p e c tiv e ly to n e m a tic p h a s e s n e a r tr a n s itio n s to th e s m e c tic A a n d
,
,
s m e c tic C
p h a s e s T h e fo r m e r h a s d iffu s e s p o ts a t q į q o n w h e r e a s th e
=

Ią tte r h a s «iifl
u s e r in g s in th e p la n e p e r p e n d ic u la r to n v e r y n e a r ly c e n e r
t ed a t
q =
į (2 7r /1)n T h e s m e c tic A p h a s e h a s q u a s i B r a g g p e a k s a ţ q -土q o n a n d
,

th e s m e c tic c
p h a se h a s p e a k s a t q İ q N w h e r e q is v e r y n e a r ly
-

2 n /(1 c o s o
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f
p o r a lig n m e n t o f a x e s T h e fu ll th r e e d im e iıs io n a l s c a tte r in g p ro lile o r
exce t f
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(b )
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i: ro n o n a n o a te m o le c u le
(b ) S c h e m a tic r e p r e s e n ta tio n
o f th e m o le c u le s i
n th e c h o le s te r ic h
p a s e T h e d ir e c to r n = (c o s k o z , s in ko z , o )
r o ta te s in a h e lic a l f
a s h io n B e c a u s e n o h s ic a l u
s ig n o f ı
p y q a n titie s d e p e n d o n th e
ı th e p h y s ic a l itc h o f th
p e c h o le s te r ic h
p a s e is p - n /k o r a th e r th a n
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之瓦 门曳

lik e th e m o le c u le s in a n e m a tic a lo n
o n d ir e c tio n d e n o te d b
g y a u n it
, a co m m
v e c to r c ca lle d th e c d ir e c to T h e re
, r in fa c t tr a n s itio n s fr o m th e s m e c tic A to
a re
th e s m e c tic C
p h a s e in w h ic h th e tilt a n l
g e g r o w s c o n tin u o u s ly fr o m z e r o T h e
s t r u c tu r e fa c to
r o f th e n e m a tic h
p a s e ju s t a b o v e a s m e c tic C
r in g s r a th e r th a n d il p h a s e h a s d ifr u s e
ï u s e s p o ts a s s h o w
n in F i
T h e n e m a tic to s m g 2 7 4c
e c tic A tr a n s itio
n p r o v id e s in s i h
tr a n s itio n fr o m th I g t in to h o w to d e s c f ib e th e
e s o tr o ic li u id
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F ig 2 7 6 S (q ) fo r q = q o n (a ) in th e n e m a tic p h a s e fa r k o m th e
n e m a tic to s m e c tic A (N A ) tr a n s itio n , (b ) in th e n e m a c p
ti h a s e n e a r th e N A
tr a n s itio n a n d (c ) in th e s m e c tic A p h a s e H e r e t (T T N A )/ T N A is th e
-
,
i i t p e r a tu r e
p e r a tu r e w h e r e T N A is th e N A
r e d u c e d te m tr a n s t o n e m

[C o u r te s y o f C y r u s S a ñ n y Ą M IT th e s is (1 9 8 1

o f in tr o d u c in g a s in g le d e n s it w a v e w e c o u ld im a g in e th e d e v e lo p m e n t o f ]n a n y
y ,

d e n s ity w a v e s (c o r r e s p o n d in to th e r e c ip r o c a l la ttic e v e c to r s a s in E q (2 5 8 ))
g
w ith s e v e r a l d ir e c tio n s a n d a c o m ie s T h e u s u a l liq u id
p le te s e t o f h a r m o n
s o lid tr a n s itio n
,
h o w e v e r , is ū r s t o r d e r (d is c o n tin u o u s ), s o th a t th e d e n s ity w a v e
a m p litu d e s d o n o t r o
g w s m o o th ly k o m z e r o

3 H ex a tic p h a s e s

W h e n s m æt i A h
p a se s a r e c o o le d , t h e y c o n den se in to w ha t w as h is to r ic a lly c a lle d
a sm «t i B b e a c r y s ta llin e B
p h a s e It is
l
n o w kn o w n th a t a s m e c tic B p h a s e c a n

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p h a s e w ith a threeimensional re a n d B ra c r y s ta l s tr u c tu
g g s c a tte ń n g a t
in a th r e e d im e n s io n a l
ip r o c a l la ttic e In s o m e c a s e s h
re c
p o in ts
o w e v e r th e
s m e c tic B ,

p h a s e is n o t a tr u e c r y s ta l It h a s h e x a g o n a l o r ie n ta tio n a l d
,

o r e r m a n if
e s te d b
th e d e v e lo p m e n t o f a s ix fo ld m o d u la tio n in th i y
e n te n s ity o f th e d i
ħıs e r in g a t
2 7t /a in th e X r a y s c a tte r in
q g in te n s ity o f th e s m e c tic A p h a s e W h
=

e re a s
th e s m e c tic A p h a s e is in v a r ia n t w ith r e s e c t to b i
p a r tf a r y r o ta tio n s a b o u t
th is /ıe x a tic B p h a s e is in v a r ia n t o n l w ith r s
y e p e c to r o ta tio n s o f 2 n /6 a b o u t
t

In F ig 2 7 7 X s c a tte r in
, g s c a n s fr o m th e m a te r ia l 6 50 B C (w h o s e m o le c u la r
ra y
s tr u c tu r e is a ls o s h o w n in t h e fi u r e a r e s h o w n fo r d ifl
g ) e r e n t d ir e c tio n s in r e c i r o c a l
p
spa ce In a th r e e d im e n s io n a lly o r d e r e d c r s ta l (w h ic h o c c u r s b e lo w 6 0 ° C
y ) th e ,

la y e r s w o u ld c o n ta in h e x a g o n a l a r r a s o f th e m o le c u le s a n d th e sc tt i
y a er n , g
c o r re s p o n d in g to in tr a la y e r c o r r e la tio n s w o u d g iv e h e x a g o n ilI B r a g g s p o ts T h e
l
s c a tte r in g v e c to r in F ig 2 7 7 is q =
(Q ll c o s x Q n s in x , Q r ) w ith X m e a s u r e d
,

r e la tiv e to a m a x im u m
in th e in p la n e in te n s ity T h e s c a n s s h o w n a r e fo r in te r la y e r
c o r r e la tio n s [S (Q JL Q O )] in tr a la y e r p o s itio n a l c o r r e la tio n [S (Q JL
= O , Q u )] a n d
ll , ,
=
,

in tr a la y e r o r ie n ta tio n a l c o r r e la tio n s [S (Q ı = O Q Q u o , x )] T h e la tte r s c a n is =

u ,

c a lle d a X s c a n A t h ig h te m p e r a tu r e in th e s m e c tic A p h a s e th e X sc a n g iv e s ,

u n ifo rm in te n s ity in d ic a tin g th e a b se n c e o f a n y in p la n e o r ie n ta tio n a l o rd e r A s

te m p e r a tu r e is lo w e r e d b e lo w 6 8 ° C th e in te n s ity b e c o m es a p e ń o d ic fu n c tio n o f
,

X w ith p e r io d s ix ,
ie ,
it can be ex p re s se d as a Fo u r ie r s e r ie s

S (Q ı Q ll X ), ,
= S ó p {Q JL , Q ll)c o s (6 P X ) (2 7 3)
P

in X T h is is th e s ig n a tu r e o f s ix fo ld b o n d o r ie n ta tio n a l o r d e r o f th e s rJn e c tic B

p h a s e T h e r e is lo n g r a n g e o r ie n ta tio n a ļ o r d e r in th e p la n e b u t n o lo n g r a n g e
p o s itio n a l o r d e r J u s t b e lo w th e tr a n s itio n to th e h e x a tic B p h a s e o n ly th e ū r s t ,

h a r m o n ic S ó { Q Q rr) is n ie a s u r a b le
, A s te m p e r a tu r e is fu r th e r lo w e r e d , m o r e
a n d m o re h i
a r m o n e s a p p e a r in th e
X s c a n s o th a t e v e n tu a lly a B r a g g p e a k
c h a r a c te r is tic o f lo n g r a n g e c r s ta llin e o r d e r o f th
y e c r y s ta lh n e B p h a s e a p p e a r s
fo r te m p e r a tu r e b e lo w 6 4 C °

T he e x is te n c e ò f lo
g r a n g e o r ie n ta tio n a l o r d e r in h e x a tic s is in a se n s e q u ite
n

r e m a r k a b le T h e b r e a k in
g o f r o ta tio n a l s y m m e tf y in th e n e m a tic p h a s e is e a s y to
a c c e p t T h e m o le c u le s c o m
p r is in g th e n e m a tic p h a s e h a v e a r ig id c o r e p r o d u c e d
b y s tr o n g c h e m ic a l b o n d s O r ie n ta tio n a l o r d e r is tiv e
p r o d u c e d b y th e c o lle c
li
a g n m e n t o f r ig id b a r lik e m o le c u l
es In h e x a tic s , o n th e o th e r h a n th e f e is
n o c h e m ic a l b o n d b e tw e e n n e i h b
g o r in g m o le c u le s a n d o r ie n ta tio n a l o ŕ d e r is a
,
r e fle c tio n o f th e lo n
g r a n g e a lig n m e n t o f th e p o s itio n v e c to r s c o n n e c tin g n e a r e s t
n e ig h b o r m o le c u le s a s d e ic t d i
p e n F ig 2 7 8 In fa c t th e h e x a tic b o n d a n g le
o r d e r c a n b e v ie w e d a s
r e s u ltin g fr o m th e lo s s o f lo n g r a n g e p o s itio n a l b u t
n o t o r ie n ta tio n a l o r d e r o f al
a h e x a g o n a l c r s ta l I d
y rr e e d th e o r ig in a l th e o re tic ,
P r e d ic tio n o f th e h e x a tiç p h a s e w a s b a s e d
o n th is k in d o f r e a s o n in g A m e a s u r e

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F ig 2 7 7 x r a y s c a tte r irıg in te n s ity fo r a Q ıs c a n (c lo s e d

(a ) x a v e r a g e d
c ir c le s ) a n d a Q ı s c a n in th e B p h a s e o f 6 5 0 B C T h e Q lr s c a le h a s b « n
a t v e to th e Q ı s c a ie T h e s c a tte r in g a lo n g Q r is a d ilħıs e r o
e x p a n d e d re l i d
'
T h e r e s o lu tio n 0 0 0 6 Å ) w a s to o s m a ll to
w id th fo r th e Q JL s c a ï ı (A G JL -

illu s tr a te T h i d i h
r e c tio n s (b ) x s c a n s a t t r e e
e n s e t d e s c r ib e s th e th r e e s c a n
d iffe r e n t te b l h
m p e r a tu r e s : (i) in th e s m e c tic A p h a s e ; ( ) ju s
ii t e o w t e

R Ħn d a k D E
r a n s itio n ; a n d (iii) w e ll in to th e B p a s e 【
sn ı e c tic A to B t h ,

M O n c to Ą S C D
a v ey, a n d J W G o o d b y , P A y s R e u L e tt 4 6 1 13 5 (1 9 8 1
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o f th e d e g re e o f h e x a tic o r d e r is p r o v id e d b y V e
ó io
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ö e an g le th a t
,

th e v e c to r b e tw e e n n e ig h b o r in g m o le c u le s m a k e s w ith h
t e x a x is
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e c tic C h
p a s e c a n c o e x is t
le a d in g to s m e c tic F I a n d L p h a s e s D e p ic te d in F i 2 7 9
,
g
, F u r th e r c o o lin
le a d s to c r y s ta llin e p h a s e s g

T h e b r e a k in g o f r o ta tio n a l b u t n o t tr a n s la tio n a l s y m m e tr is r e fl
y e c te d in th e
p a ir c o r r e la tio n fu n c tio n g (x , x ) B e c a u s e tr a n s la tio n a l s y m m e tr y is n o t b r o k e
'

n ,

th e d e n s ity <n (x )> =

(n ) is in d e p e n d e n t o fx ,
an d g {x x ' ) = , g jx x
'
) is a fu n c tio n
o f th e d iflfe r e n c e y = x x
'
=
(y L , J ll) H ow e v e r b e c a u se ro ta tio n a l sym m e tr y is
,

b r o k e n g (y ) is n o t fu tio n o f y ly l ly R a th e r , it be
, a n c = o n ca n ex p a n d e d in an
an g u la r Fo u r ie r s e r ie s ,

ó ip u
g jy ı y ir) =, g o (y L ý ı
r) ,
V óp {ý ı , Ji ll)e , (2 7 4 )
P

w h e re 9
o d yı - 1
(y ı O ) in p o la r c o o r d in a te s T h e p a r a m e te r s V ó p {y JL y ; )
a n =
,

lik e S ó [E q (2 7 3 )] to w h ic h t h e y a r e r e la te d m e a s u r e th e d e r e e o f h e x a tic o r d e r
p g
W h e n y ı is e q u a l to th e a v e r a g e in p la n e n e a r e s t n e ig h b o r s e p a r a tio n a n d v O -
l
ió p o . $
V óp is e s s e n t ia lly <e > h e r e 0 . F is th e
,
w a n g le th e v e c to r c o n n ec tin g n e a r e s t
n e ig h b o r m o le c u le s a a n d þm a k e s w ith th e x a x is A d e r iv a tio n o f th is re s u lt is
o u tlin e d in P r o b le m 2 8

4 D is c o t ic p h a se s

T he tic a n d s m e c tic p h a s e s ju s t d is c u a te r ia ls
sse d g e n e r a lly fo u n d in m
n em a a re
c o n s is t in g o f ro d lik e m o le c u le s P la te lik e ra th e r th a n r o d lik e m o le c u le s su c h as
th o s e s h o w n in F ig 2 7 10
c a n fo r m d is c o tic n e m a tic p h a s e s in w h ic h th e p la te ,

a is li
a r e a g n e d a s w e ll a s
p h a s e s w ith c r y s ta llin e o r d e r in tw o d im e n s io n s
n o rm
,

d li id lik e o r d e r in th e th ir d d ir e c tio n F i 2 ? 1 1
) T h e la tte r a r e c a lle d
a n qu ( g
t
c o u n n a r T h e p la te lik e m o le c u le s
s e g re g a te in to c o lu m n s w ith th e
p la te n o r m a is
e ith e r p a r a lle l to o r tilte d a t a n a n l
g e to th e c o lu m n a r a x e s T h e r e is n o lo n g
ra n g e p o s itio n a l o rd e r w ith in a c o lu m n T he c o lu m n s th e m s e lv e s fo o f th e
rm an y
tw o d im e n s io n a l c r y s ta ls

5 L y o tr o p ic liq u id c r y s ta ls a n d m ic r o e m u ls io T ts

In th e p r e c e d in g d is c u s s io n ,
w e h a v e fo c u se d o n liq u id c r y s t a ls w ho se p h a se s
c h a n ge in r e s p o n s e to c h a n
g e s in th e te m p e r a tu r e T h e y a r e c a lle d tlï e r m o tr o p ic
liq u id c r y s ta ls L iq u id c r y s ta llin e h
p a s e s a ls o a p p e a r in r e s p o n s e to c h a n g e s in
c o n c e n tr a tio n s o f w a te r o il f
s u r fa c ta n ts o r o th e r s e c ie s in a w id e v a r ie ty o
, ,
, p
l l
m o e c u a r m ix tu r e s T h e s e a r e c a lle d l o tr i li ll
y op c q u id c r y s ta ls a n d a r e g e n e ra y
fo r m e d b y a m p h ip h ilic m o le c u l he r
e s c o n s is tin
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a n d /o r a r e s o lu b le in d iÆe r e n t
s o lv e n ts T h e m o s t em s
w id e ly s tu d ie d o f s u c h s y s t
a r e th o s e c o m
p o s e d o f m o le c u le s c a lle d lip id s w ith h d r o h ilic w a te r lik in g )
"
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"

p p

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(a )

(b )

F ig 2 7 8 \ S e a r a te d r o u s o f n e a r e s t n e i h b o r a to m s in a h e
p g p g x a go n a l
c r y s ta llin e
p h a s e A to m s o c c u p y ı a ttic e s ite s o n a tń a n g u la r la ttic e , h ıd ic a te d
b y g r id lin e s E a c h a to m h a s s ix n e a r e s t n e i h b o r s fo r m in a h e x a o n i
g g g n
o ń e n ta tio n a l r e is tr
g y w ith th e la ttic e T h e r e is b o th lo n g r a n g e tr a n s la tio n a l
a n d o r ie n ta tio n a l o r d e
r T h e fig u r e a t th e s id e s h o w s th e h e x a g o n a l pattern
o f B ra g
g p e a k s in th e X r a y s c a tte r in g in te n s ity a t th e s h o r te s t r e c ip r o c a l
la ttic e v e c to r s b S e
( ) p a r a te d g r o u p s o f a to m s in a h e x a tic p h a s e E a c h a to n ı
h a s s ix n e a re s t n e ig h b o r s fo r m in g a lo c a l h e x a g o n D is ta n t h e x a g o n s h a v e
th e s a m e o ń e n ta tio n r e la tiv e to s o m e fix e d a x is A to m s d o n o t h o w e v e r
, ,
O c c u p y s ite s o f
a tr ia n g u la r la ttic e T h e r e is lo n g r a n g e o r ie n ta tio n a l b u t n o
lo n g r a n e o s iti
g p o n a l o r d e r (w h ile th e o r ie n ta tio n a l o r d e r w o u ld b e e a s y to
u n d e r s ta n d if
th e p a r tic le s w e r e o n a n o r ie n te d s u b s tr a te o r c o u p le d w ith
tr a n s la tio n a l
o r d e r o r ie n ta tio n a l o r d e r o f s h e ń c a l a r tic le s is r e m a r k a b le in
, p p
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e n e ith e r a s u b s tr a te n o r c r s ta llin e o r d e r is
y p r e s e n t a s in th e c a s e
s c tie m a ti
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g y s c a tte r in g
m te n s it fr
y o m a h e x a tic p h a s e T h e in te n s ity h a s a s ix fo ld s y m n ıe tr y b u t n o
B ra gg e a k
p s T h e s c a tte r in
tw o d im g in te n s itie s a r e fo r th r e e d im e n s io n a l s y s te m s In
e n s io n s flu c tu a tio n s a s w e s h a ll s e e in C h a te r 6 m o d il th e s e
in te n s itie s , ( p ) y

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f T T
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Sm ec t ic I Sm e c t ic F Sn ıe c ti» L

F ig 2 7 9 Sc he m a tic r e n o f lo c a l h e x a g o n a l c lm te r s in tilt d
p r e s e n ta tio e
h e x a tic p h a s e s In th e s e p h a s e s , m o le c u le s a r e tilte d r e la tiv e to th e la e r
y
n o n n a ls a s in th e s m e c tic C p h a s e E a c h m o le c u le h a s s ix n e a r e s t n e i h b o
s rs
(w h ic h in g e n e r a l o c c u p Y p o s itio n s o n a d is to r te d r a th e r th a n a r e g u la r
h e x a g o n ) In th e s m e c tic F p h a s e , th e c Ą ir e c to r p o in ts to th e m id p o in t o f th e
b o n d c o n n e c tin g a d ja c e n t n e a r e s t n e ig h b o r s (i e to n e x t n e a r e s t n e ig h b o r s )
,

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p h a s e it p o in ts in a d ir e c tio n b e tw e e n n e x t n e a r e s t a n d n e a r e s t n e ig h b o rs

SR

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F ıg 2 7 10 S o m e p la te lik e m o le c u le s fo m in
ı g d is c o tic liq u id c f y s ta u in c

p h a se s

o r tw o h yd ro c a rb o n c h a in s co n ta in in g 8 to 2o c a rbo n a to n ı
s T h e h y d r o p M lic
h w n
g ro p g e n e r a lly h a s a
u c h a rg e o r a d ip o le m o m en t E xam p le s o f lip id s a r e s o

in F ig 2 7 1 2 (p 7 2 )
w h e n in ta c t w ith w a te r , lip id s w ill s e lF in to in w h ic h
co n o r g a n iz e s tr u c tu r e s
s
h y d r o p h o b ic ta ils a fe s h ie ld e d fr o m c o n ta c t w ith w a te r C om m o n s tr u c tu r e
d
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n ı llw in v e r te d micelle b ila y c r s h e e an
l
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o
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s tn ł
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(b )

(c )

F ig 2 7 1 1 P la te lik e m o le c u le s in (a ) ヒ d is c o tic n e m a tic , (b ) a h e x a go n a l

c o lu m n a r d is c o tic a n d (c ) a re c ta n g u la r c o lu m n a r d is c o tic
,

p h a s e s , in c lu d in g n e m a tic , la m e lla r (s m ec tic ), a n d c o lu m n a r p h a se s A p h a s e

d ia g r a m s h o w in g d ifle r e n t e q u ilib r iu m s tr u c tu r e s is sh o w n in F ig 2 7 14 (p 7 4 )
A n am u s in
g ex amp le o f a p h a s e w ith th r e e d im e n s io n a l c r y s ta llin e s y m m e tr y
(c u b ic ) is th e p lu m b e r s n ig h tm a r e p h a s e s h o w n in F ig 2 7 1 5 in w h ic h th e r e s
" ' " i
a s in g le co n n e c te d b ila y e r s u r fa c e s e p a r a tin g tw o id e n t ic a t w a te r r e g io n s

T h e h y d r o p h o b ic h d r o c a r b o n ta ils o f a m p h ip h ile s a r e s o lu b le in o il, w h e r e a s

y
th e ir h y d r o p h ilic c h a r g e d h e a d s d is s o lv e in w a te f A m p h ip h ile s c a n , th e r e fo re , b e

u s e d to c r e a te e q u ilib r iu m b u lk m ix tu r e s o f w a te r a n d o iıb y p r o v id in 吕m o n o la y e f
in te r fa c e s b e tw e e n w a te r a n d o il T h e se e q u ilib r iu m m ix tu r e s o f w a te r , o il, a n d
s u r fa c ta n t (th e a m i h s im ila r
p h ip h ile s ) a r e c a lle d m fc r o e m u ls io n s T h e y e x h ib t p a s e s
to th o s e o f w a te r li id m ix tu r e s A ]a m e lla r b ic o n tin u o u s
p p h a se a n d a r a n d o m
p h a s e a r e d e p ic te d s c h e m a tic a lly in F ig 2 7 16 (p 7 5 )

2 8 0 d tw l o rd e r in
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th r e e d im e n s io n a l m a te r ia ls

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c o n s titu e n ts o f c e ı
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sp a c e d m a ss p o in ts ca n be c a lc u la te d fr o m th e d e n s ity fu n c tio n

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n d
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p e ń o d ic p lu m b e r s n ig h tm a r e p h a s e [D M A rıd e r s o n , s M G r
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p w t w a te r 0 a iıd
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u o m

r e g io n s
se p a r a tin g o iıa n d w a te r

w h e re x =
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,
p o th e o r ig in o f th e
p e r io d ic a lly s p a c e d m a s s e s o n c h a in I T h e s c a tte r in i
g n te n s ity is

(2 8 4 )
W Q
w h e re [ ] s ig n ifie s an a v era ge o v e r th e v a r ia b le s ￠ı If n e ig h b o r in c h a in s a r e
g
u n c o r r e la te d th e n
, w ill b e an in d e p e n d e n t ra n do m v a r ia b le a t e a c h Ła n d

if ą z 一 0
T he su m in E q (2 8 4 ) c a n n o w be e v a lu a te d ,

Th th e r e
g g p e a k s in I (q ) w ith in te r Įs ity N īN in th e p la n e ą z
lB O Ñ
a r e re a ra =

th a t re a e c t th e twoimensional la ttic e o f c h a in s In a d d itio Ą th e r e a f e B r a gg

s h e e ts w

fe
ith in te n s it N
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e r a lo n g e a c h c h a in A w a y fr o m q z O th e u n c o r re la te d =

c h a in s lo o k
ju s t lik e th e s in g le on e i me n s io n a ] c h a in b u t w ith a la r g e r in te n s ity
A s c o rr e l
a tio n s b e te d a s
tw e e n c h a in s b u ild u p th e p h a s e s ￠ ı c a n n o t b e tr e a
in d e p e n d ,

e ııt ra n d o
m v a r ia b le s o n e a c h c h a in , a n d th e a v e r a g e in
E q (2 8 5 )
d e v e lo s
p a n o n ze ro v l T h e s e c o r r e la tio n s le a d
a u e fo r ı+ ı e v e n w h e n ą z + o
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F ig 2 8 1 (a ) A o n e d im e n s io n a l e r io d ic a r
p r a y o f p o in t s c a tte r e r s w ith
d e n s ity g iv e n b y E q (2 8 1 ) a n d (b ) th e s c a tte r in i t
g n e n s ity in r e c ip r o c a l
s p a c e w ith d e lta fu n c t io n in te n s it
y o n s h e e ts p e r p e n d ic u la r to th e c a x is

F ig 2 8 2 X r a d iflu s e
y s c a tte r in g p a tte r n fr o m th e o r g a n ic c h a in s a lt
M N T S F T C N Q s h o w in
g o n e d im e n s io n a l o r d e r T h e d ifï u s e lin e s b e w
t een
th e ıin e s o f B r a g tio n
g p e a k s a r is e rr o m o n e d im e n s io n a l o r d e r T h e m o d u la
in th e in te n s it o f th e
y s e lin e s a r is e s fr o m c o r r e la tio n s b e tw e e n
o n e d im e n s io n a l c h i
a n s [C o u r te s
y o f J Po u ge t]

to d iflu se s p o ts o f in te n s ity in th e tu a lly

p la n e s o f th e B r a g g s h e e ts th a t even
d e v e lo p in to t r u B r a g g p e a k s w h e n lo in s
e
n g r a n g e p h a s e c o h e r e n c e b e tw ee n cha
is e s ta b lis h e d
T he bo d is c d ic
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F ig 2 8 3 T h e sc a tte r in g in te n s ity fr o m a o n e d im e n s io n a l s in e w a ve de n s it)

co nfin e d to th e z a x is [E
q (2 8 7 )] T h e r e a re tw o B ra g g p la n es a t q - į qo
bu t n o B ra g g p la n e a t qz 0

o n e d im e n s io n a l s o lid s W e w ill s e e in C h a p te r 6 th a t t h e r e ca n be n o lo n g ra n ge
o rde r in a o n e l s y s te m (w it h fin ite r a n g e fo r c e s ) F lu c tu a tio n s w ill
d im e n s io n a

c o n v e r t th e id e a l B r a g g s h e e ts in to d iflu s e s h e e ts in r e c ip r o c a l s p a c e S in c e m a n y

s c a ttėr in g te c h n iq u e s lo o k a t a p la n e in q s p a c e t h e in te r s e c t io n o f th is p la n e

w ith th e d ifï u s e s h e e ts a b o v e g iv e s d ifï u s e lin e s C o r r e la t io n s b e tw e e n c h a in s

w ill c a u se v a r ia in te n s ity o f th e d ifï u s e lin e s w h ic h a s d is c u s s e d
tio n s in th e ,

a b o v e w ill b e c o m e B r a g g s p o ts w h e n lo n g r a n g e c o r r e la tio n is e s ta b lis h e d T he

,

d e v e lo p m e n t fr o m d iffu s e s tr e a k s to B r a g g s p o ts is illu s tr a te d fo r a n o r g a n ic
c o n d u c to r M N T S F T C N Q in F ig 2 8 2 T h e o n e d im e n s io n a l o r d e r in g is a
li b e tw e e n th e
d e n s ity w aveg in d iv id u a l c h a in s in th e c r y s ta l T h e c o u p n g
a lo n

d e n s ity w a v e s e v e n tu a lly le a d s to t h e ir th r e e d im e n s io n a l o r d e r F o r th e c a s e o f a
s im p le o n e d im e n s io n a l s in e w a v e t h e r e is o n ly a s in g le p a ir o f d ifï u s e s h e e ts a s

sh o w n in F ig 2 8 3

(n (x )> -
p o ô (x )ô (y )s in (ą o z ) ,

N o te th a t a sm ec tic w ith its re a lp e r io d ic c h a in in

sp a c e la y e r s p r o d u c e s a

r e c ip r o c a l s p a c e in th e s a m e w a y th a t a p r o d u c e s la y e r s in
r e a l s p a c e c h a in

f e c ip r o c a l s p a c e A ls o ju s t a s fo r a r e a l s m e c tic w h e r e o n ly th e fir s t h a r m o n ic is
,

i
p r e s e n t a n d o n ly tw o s p o ts a p p e a r in t h e s c a t te r in g fu n c tio n a s in g le a r m o n c
h ,

w a v e in o n e d im e n s io n
p r o d u c e s o n ly tw o d ifru s e s h e e ts

2 9 In c o m m en su ra te s tr u c tu re s

T h e re a re s tr u c tu r e s in n a tu r e th a t a r e n e ith e r ra n do m p e r io d ic b u t th a t
n o r
h ibit s p a tia l io d s S tic h
r e r e la t iv e ly ir r a tio n a l p e r
ex d
m o u la tio n s w ith tw o o r m o
s t m n c tu r e s a r e c lle d q u i p e r io d ic T he y a ll r e s u lt fr o m c o m p e t itio n b e tw e e n
a a s u su y
tw o d ifre r e n ļ le
n g t h s c a le s
A n l r o d u c in g iï ı
exa m
p le o f a s y s te m w ith tw o co m p e tį frg le n g th s c a e s p
co m

m e n s u r a te to m s a d s o r b e d o n
s t r u c tu r e s is t h a t o f n o b le g a s (X e K r e tc ) a, ,

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