: . . . . . . . . .

, , , , , ' . ,

. . . . . . .

t. t ~ t ~ , t t ~ a

.eke e x ~ - ~ e t ~ - e ot'h~et~ ~ dxe a~oqnioa bothem~

.Of t h e . the tt~.'lpu3t>o~.'~ by' t~¢ Ol~'vkt~ at~t
Gdt~tl~ L 6 ] b ~ beer tee tao-~t~ u ~ ' , . ' s ~ t ' u l . R~.eafl~. o~er t:,a~r for ~mnsi¢~ ~ ~ ± e ~dsor~
a tttttRbcrQt~wo~ket~ha.~ $/,ttQ,~-~ t [ ~ triode| in ~e. tton ~ t b e m t . We h ~ e a h o ~ e d the vadatioa o f : •
m~aa-t'~t¢ ~pt~xtmatt~a 1 6 - , $ 1 a t t d bY Monte C~to the shape o f the p o t e n ~ e n e ~ " cur~e.witk prepare
,/mulatloa [~l.1O|. lu tbi~ mo~el, thet~e~ion abO~ the and t~mpet~tm~e. " "

sub,Irate i~ d~kied t u t o a ~et ofcell~. Akth celt ht the.

/th la.x'¢ri~ descdbe~ by n/~. which ~ 0 if the celt i~ •
uit~.n~'upied and t if~n:upik~, E~.'h amta ~ , ixttemcts
with it~ x~ac'-~-~t~ishb<mr~ anti the substrat~ with an . i • ' ". . .

cu~r~ ~ - e ~ 0~, r,'/ve,'tt~b', wt~ee e~v~- - ~C,:~ tbr In the mean-t"~d_app~.~,ation..me e x p ~ o n

/~'-lattdeOfor/ffi:t. . ' ' ' .- .. - for the free enet~,.~2 ~~t~ea by [ 6 ]
• The comp!et¢ Hamiltonian is given bY

, ] ~ I $ "

where/~ i~ t h e potential o f t h e ga~..

c l ~ u i c a l

. hi the p ~ n t w o ~ x~ have solved this model in : : (2)

the meau-t~|d app~xhnatiqn by a umnerkal method • Heze, p t ( O ~ p i ~ l}isthe m~ragevMueofntk f o r t h e
diff¢~mt i't~m tho~ used by .earlier worken~ [6.-8]-- in l'th laYer, L - is the nmnber o f cells in a ~]ngle layer
hax'inga neat~t neiMhbountwithh the layer andb
Qontn'butlon~o. 2 ~ from the ~ State and S'a.u~m.ml ...ne~-est n e ~ b o u n in the h y e r j ~ abo~.i~k is m e "
chem~uy Unit. '• . .. ' " . Boltzmann constant and Tis.the temperature+ ".
. . . ' .

265
~O~4-~mno et~.~x~ e U ~ . m v i s i o n )
 .. . . . •

•
. ..
. . .
..
. • . . .
• . ... . ". ::.. . ...

t,~~vi'~h.r~speet to c~w,~m,,e~~att 1~ obtahtt~f as

.. • ~ ¥ , Thus, a t T ~ L 0 a ~ l A~ ~ - - 4 8 fox~V --. 25,..
• ..t00, $00 ~ d 1000, the I o o r R l m ~ o f the d i f f ~ n ~ e . . '
between th~.~Vtt(.!~er ~verage and the,.'o~emge o f . ' •
. . . . • •
the l ~ e r at tut'mit~. (u (mA.- m . ) . ~ , e . 1 8 . 3 3 . • .
- 2 2 . 4 9 . - 2 7 . 4 7 and -31.28. Further. b ~ this method .
~.= 1. ' " " " t3) w ~ ha~e b ~ n able to o b t ~ all the solutions of the set
whc,c m i ~,/-'-.t .(- l ~ m 1 ~ D, The ~alu¢ o f m 0 is o f c o u p l e d ~ l u a t t o ~ (3), lu our ~ ¢ u l a t i o ~ we have
laK~,°tt l~ be - l , ¢ouesp0nding to an t t u ~ e / ~ z cloth used C = 4 . 2 , . D = 7 ~ S , $ . a n d a hexagonal latttce.a -- 6
1~3~'1. So, R'l~t ! is RU~x~U,lh;,~ k ' o t n p l e w . ~ l u t l o n is and b = 3, as us¢~1 b y eadler workevs [6-I0l.
[ u o ~ n,. b t ptiticipl¢. Be.low, ~¢ describe the numerical
tnelti~l USk'~lby tlSfOl~obtainitkll the multiple solutio!l ." : '..

or" the ).'t ofequatious i3). .... ' . ' " ..

•
'l',. ,, re. ,he (;,, is a,, ,, . ,
. . " .

sumed. Coye~a,~,esofhlgher I~els ml J i f - ."~ . .-I, . . . . ate •

la ¢ertah~ regions o f pt~sute and rempemture, we

computed from ,,'Se above.. equations until some m/has have found three solutions.-- two minin m and.one
g o u e OUt o f the range I,-1. l). If{m]~ r is $reater than
nmxhnmu. If.we follow the two solutions con~p0nd-
+ ! then we.s~t im ~}~, =. (m,)~, and lo0k tk~t another. ' ' ing t0 the two minima, the coverage venus chemical
(m ~~ such'thai t't~r .,,'omej¢(mi.), < - 1 and Set
- . J '~ " " . " 1 . t . r . potential Shows a.clear hysteresis effect (fig. 1). as.
tm i),, = I m I ~ . The ~x~rt~t value o f m t lies bt the seen in the Monte Cad0 simulation of.this problem by
.in.let~al tim I .lu- I,m l ")It),
+ The" new tthaix'alue for m l
.

Kim and Lalulau [9]. indicating the existence e r a .

L~ t h e n • :. .. first.order transition~ OUtSide .the range o f hysteresis
= It,,,, + t,.t),ill2: oMy one solution could be found. In earlier m e a n - .
t'ieliI treatment s Of thi s problem, a single solution at •
,. l,i..h ,el, > + 1or t,,,, it" " all.temperatures and pressures was obtained and. con-.
% . I. 'l'hk it~,ralR)n is continued until (m i)~r - (m I }~r sequent[y, no hystezesis.wa s observed.in the adsorp: ..
' ~" ' I~ ~ • .~ • ' ,~ . • t
is ! ~ t!lan !t.)"' " . k a d h ~ to aycry a¢cttrat~ value for.. tion isotherm [6,7 I. As the temperature is ~ , . w e .
m I ..With the" value 0fro t known,.a shnilar iterationis find the .iegion Of hysteresis contracts and finally
!~'1l\~nued t\~r the ~o,~nd lay.at and its value detemdn- • vmdshes entirely at T - Tc . allowing coverag e to vary.
ed."rhL,,, t'.~.~.'e.~ i~ c o n t i n u e d f o r e v e r y l~3,'er tO d e t e r -
continuously (f'l8. 1).
mine thecoveta~es to a ve~, high degree ofaceumey.
.We have plotted in fig. 2a the energ..v for t h e t w o
Ibis .~'ems to be nccex:sary as a ~uall error in the value solutions against chemical potential in the region where...
ofni~ in one layk'r leads to a vel'~' laq.'e and rapid error the first layer becomes co~iered at T = 1.0 *. For A/~e •
accunlulatkut l\~r sub~queat layers.Thus. w e have ' > - 4 . 4 4 and for A / t / e < - 5 . 2 8 , t h e r e is a single solu- ...
estimated that au crook,of I0" t$ in tl~e fir~t-Hyer '
lion. c o r r e s p o n d ~ to .the t~.'gion.outside h wteresi~. : .
cox¢tagy can lead it) an error (~f 10 - 6 for the ~.~.'ond. In.the. region o f hysteresiS, - - 5 2 8 < A / ~ e < - 4 . 4 4 . . .
laver ,.'overage. . there exist two solutions. The two lii~es con~.~sponding
rills meth~xl ot',~)lvi~kt cq. [3) has the advantage to energies o f t h e s e . n ~ solutions intersect a t A p J e
• that a ~'el'y iarsx" uumber.ot'layers,~V, c a n be handled • , 4 . 8 5 . This corresponds to the dashed tr~n~;tion
~itl{ ~'e,y little 0,unputer time. This a v o i d s the neces- line shown.in f'tg..l~ and detem~inesthe transition p ~
" s i t ) : o f truncating the nmuber o f layers to an)" miall
sum obtained by Other w0~ken [6.7] in their mean-
,-,lue b, n done earner Infact. this meth- field solution. In fig.2b ~ e have shown the chemical
. (,~thas.Il,r adr,tma$~- of bein~ ¢nlk~ly.t'tx~.from an>" "..
p0tentkil versus eneigy plot for T = 1.4. The ~ e be- .
•tmu,'~tkm eflk'cts[t~l as the.~lutKm Is independent . •
t w c e n the two energy i~es. O, is 3 8 3 ° at T = 1.0 and :
of the number of l~.ver$~'on~idetx'd.Moreover. in tltis " .. .' .'.

medical ~'edo n o t have to t\~t~'e any finite layer tO . • . • ."

have the ~xwet'~.,e o f m , . theway other workers had. • The temperatu~ F b in units o f k l r ' / e . ' '

" 2t.t',
 '. ": .. '

• • . .. ' ' '... • .."

.. ' . '. ".. ' . . ' . . ~.~ -- .

i i

" ..

. t3.. .

,. .. .. _~. :. .

- , - - : . . . ,,. ..

I I ~ i-" + I
-~.Z -~-~ -5-0 -5.t,.. -0.7. -0.~ -1.0 • -0.1 • --0.3

aW( . • ..

'." .. ' ..

F.f~. 1. C o w r a ~ as a function of chemic.Jl potential at ~urioustemperatu_~s f o r ( a ) f i r s t . Co) second and ( ¢ ) t h i r d la~e.ts, s h o w i n ¢ '
• hysteresis curves determined in the mean-field approximation. Open circles indicate, co~ed solution and filL'd drc~s fndic~ze un-.
• c o v e r e d sOlulrJon. ,. .•

' • " ' " ' I' '. "

• oO.S; -

. : ,0

' . " ' '' '. " , l ~ " . . .

-- 021 .. /
..

' .' 'o.,o~ .. {cd . .. . ~ /~

~o ' T=I-O /: [b}
•" . " .. r .'. ' 1"= I.~.'

'Eli. . ,,.e-I..o- 623 ~-¢e "~ "

• .
j .. .. ~ I.
o . p sQ

I .- /--
-O.r., . . . . o,~" . . . I. '
... .. : :+._ . : •
. . . . .°'=" • .. : . .. 0.2 ~ , . , :/- . ... . ..

.. ! .. . |
--4~ "'-&-8 ' -5.2 .: - ~ - [ 8 2 .. - - ~ '
"-~.gO
•
• ..
. " AFJ~ ' .. ..
"v-~
. . . . '.'. . • • ... . '. .'. . . . ..

• F ~ . 2. T o t a l e n e ~ - a s a function o f t h e chemical potential for the t w o s o l u b o m Which ~ zis= t o b ~ e r ~ ' ~ O p e n c-';,.tesxeIa~- ' "
seat cm~d.~e~.n and ~ drdes repLl~eat uneQ~ed s o l u t i o n . A n o w , , ~ , , ~ - the chemical p o + + . . ~ . l E ~ a , t h e t w o Hnes..
;,,,t .e.,.mct+ om'espO,,,~r,',-,'.to T J ~ d o u e d m, e s s h o w n ~, f f ~ l.. • i s .~be ,, _,,~. l x . n r e , = t h e t w o rmes z i d~e p o b ~ o f ~ e z s e c ~ n . Br~r--n .
Hnes are drawn onl~" as a suJde to the eye.. , , , ' " , ' , " ' ,, • ,, , ' : ., ,

267 '
 ,.' ..
• . '.," =
mYstcs L m - m ~
i

C~CAL ~ . S ~ !9z4

~'~3,0* at T:, 1.4. The :t~de between tl~ t ~ eaer~"

l~ d~t~ w~th an h-~tx-:,~ tu.wmpemtu~:. In fact, . Q-4. .'.. ' .... "' .

~ e |~t~dthat ~ decte&~s c~ntianou~ with i n ~

tcmpemu~e..~it~ t o ae~ at T : T c ( s e e r~..3~). be-
•I/ A~.=-~Z
h~'b~ ms at~ ~ e r p a r ~ t e t e z . . ' H m . ~ a s ~ approaches
~ x a t~m.or4er tm~'tten goes o ~ r to a secotel-o,r-.
de¢ tr4~t.~ltkmat T : Te. The bebavtourofO for the "
,V °.IJ
~ 7S.. ~ t . I. / .

,<t'xx~t~l.hyet ~s~ o w n ~u t~., 3b~ We flt~ that ~ e higher

l:.~'et~ ha~e h~Jxer cn'tical temperatures, in accordance
~i~h e~xBer f'n~ia~s J6.?l. Hisher layers ba~.~ lowec "
7A-v
~tt~ot'O for a,~twn temperature.However, for h~her
I ~ e t ~ 0 de¢~ases mo~e s~oWb" with an bic~ease in" " °"+ o;/.". "! ' :
~empe~at~.tesub~.~ ~ h~her T~.~ue~ (r~_31. At ~1" ~i~__~ 1 ~IlI III I I I [iI~ll~i ~
this ~ t t . X~ note that. E~r a moze p ~ e descriptOR. , ¢/ ,y ko,
: O s h ~ l d be ee~qa~d b~" the d i ~ e n c e t,i the slope at
• . . ~ . ' ~-~- . I ./ .. "4. I L ' .
t h e tUtltSilk~n p t ~ t t t ~ . O f t h ~ t w o lhxes. ~ " J-- " I .~-.+"
•. ~.i-~.--~ --~..-~'~ +' " . . o.¢ . ~. ..
" "t'h¢abox¢ ~suhs¢m~ be beuer uu~er~toOd by look-
h~ at the potential ~II¢lll~"~ t . l $ k'owrdge plots deptcb
~xt in i't8~4~The apptxxxima~e potenthl-enetT.y curves • ' / " ~ ,, , ~ " :~I\ - /
0d=- . ~ .-0.z r, .N./ . I ~
~ obtained as a t ~ t K m 0f the ~.'ovemb~.m~ of ~I ~ I ' : i i III ~ IIi III;Ii'
I QIQ~I I' I i i I i ii
t'~tttk'~lla~ l a y ~ j~ by a..-~smlth~f,t~lFg£ : 4"0.99. (lower •
l~.~'CtSlteatb" t'tU+.xi)attd mi>~ : . 0.99 (upper layers " .IZ...~ ' .._..~.~ • " . ."
x~r~" empty), This is e.xp~.'t~ to "~tOWt~li.a.blet~nd~.. ' .f

pa~tk'Ulatb" below.T~ as with F ~ T~ I~'evs ate bt- . 2 "0

~kx'd fiR~ ~queutially. The results for the f ' ~ t layer
~ F : i,0 a~. "shown hi fit~,4a, e~ml. b ~'aHed between -I -5 -I -1 -I . -1

Iattd + I, ;he potendal-enerf..v Cmxe s h o ~ a single "' taJ ' Ibl ~i ..'"
tl~ittitnutxt a t ¢,e I . . . . 0 . 9 tk~ . ~ p ~ e < - " 5 . 3 w h i l e in the mI
hystet~,~islt.'~K~nat ~ ! e : =,~.. there at~ two solu-
Fig. 4 . F o t e n t h l e n e r ~ , as a t'unction o f covetable at ~'a_rious
v : l - ~ o f c6emlc.~l p o t e n t i a l a n d t ~ m p e m t ~ ( : ) 7 " : LO. Co)
!.1 -.,rid (¢} 1~- . • . . ."
' ze~ tel
ttom,Soin~vhe= in the mtddte ofthe K~eres~ ~
igton atAl.~ve = -4.9, the P0tential-energy euxve has
17 11, 1.~
two deep well-defined mininm. With anin¢i'easein
•'.lp/e to--4.4,, the p0tent!al-ene~Y curve 8iyes rise tO
' . . '.'
a single minimUm again but at =~+0.9.
In figs. 4b and Ac we have shown these plots for.
i T = I.I and 1.5. With an increase in temperamze the
•, ie,}
e,~¢ 3~,~.~'~-,,,. minhna become shallow. Also. the diffezence tn ener-
l % gy be(ween the two n6nima decreases, cort~'P0nding
~o O. approa~-b.in S z e r o . A ~ 7 " = = T c t h e r e is a s ! n s l e m i n i -
\ ." mum for all A/~. leading to an absence o f hysteresis.
'.
.. .
.
IZ
1

Y
."
t

t '
t'

16
. "

This mininxum ~/es continuousl.vfmm --I to +I as

.'T ..
..
die pressure is i n c r e a s e d . . .
, .
:
• . '

.I-.i~.: 3. V=tiati~a ~t" l h ¢ = a t : l e b e t ~ n t h e t w o en~Pf.y l i n e s

with teU~pe~atUze' the ia~ l ~ t "~=d tb~ se~x~M l:~'ers. Dashed
li~t~"~ dr~wtt Io SuMs." t h e eye. ...

:bS
• vo~e ne,,.,-T~.3:
• . . • . • . . .

4. ~ o a d m i o a i~efes'ew~s
. . . . .

" w e ha~.'e,soiVedt ~ ~ equmiom ~ - a "~- "ltl C F P~-,~vqw a ~ G . D ~ J 2 y Jr., J.P~y.s. C ~ = L 61

m e r k a l m e t h c d which gi~es muh~ole solutions in cer-. (!gYD It,S:
t~tn ~ £ 6 o r ~ o f p t ~ u c e ~ t .mm~.~ ~ A . T~-~--, l . ~ l l o k l l . - ~ - , - ~ e S d . ~ r . ( 1 9 7 D 836; •
6 s e to h y s ~ e x e ~ in the. a d ~ r p t i o n ~ r ~ + ~ - ~ A pa-
f1975) ~4.3:
mmete~ has been found W h i ~ ~0es m ~ m as T~- T ~ •A.'l~om.w ,,,,,! X. Dural j . t - x ~ , Ira-j~. 67 (1970) 286:
•f0r the~th la.ve~, b e ~ v ~ g like an o ~ e ~ pat~ueter. F_.l. P;.u~u~ and T- Ferc Jr_ $. ~ ~ 7 9 (1975)
.The p o t e n t ~ l e ~ e r ~ as a fh-*'~iono f c o ~ s / ~ " ~ ' 459. • ..
t w o m ~ t m = ~ thelt'esion O f t ~ m p e ~ and pt'e~u.te 12l T.I_ wra J . ~ T s . IS (I94T) 7 6 7 . '
[31 W-~LCk~uion Z l G.D_ ~,t,-w Jr... J. P'nyL C"~wn.~57
where ~ ' s t e r e ~ is found and a ~ e m~n~'num in.the
(I~---"~ &.{..6..
region w~exe n o hystet'esis is observed. '
[ s l D - ~ - . ' C e ~ m e . J . ~ e - ~ - c ~ - - 7S ~X974)26e0.

Acknowledgement • (I978) 687.

[7"i C_E'oner.Ph'ys.Rmr.A22(1980)Lr/76. , . , ....
[8l R..I~-m'-,.i'.M.Sd~k andM..Wor'-~t~ys.R~.B26 "
Tl.te m t t h o r s are &~atefuI t o P c o f e s s o r C 2 ~ . R . R a o . (XgS?_)51XZ . . .
•'for kind e n c o u r a ~ m e n t and vaIuabIe d B c u ~ o n s . [9[ I_M_ t--,~ ~,,d D.P_ r ~,,.,.v.,, $ ~ o ~ Sei_ I ! 0 (ig~tl) 4 1 5 .
[ 1 0 | C. Elmer. l~.-s_Rmr. A23 (1981) t 9 ~ .

269