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The fourth virial coefficient D and its components D1, D&, D3 for molecules interacting with a square-well
potential have been obtained as functions of the temperature by the use of Fourier transformation and the
addition theorem of Bessel functions. Each component and their sum are nearly constant above the Boyle
temperature and tend to negative infinity as temperature tend to zero. The total D is expressed by
D/b'=0 28642+. 1 5397f . 23.55
4f +53 1ft 14.777fe
645f'+. 69 859f' .170.0
where f=e'ter
1, and well width is equal to the hard core diameter. Corrections of the critical data and
some related problems are discussed.
L~)
I I
E to to) I
experiments. "
We denote the position vector of the
ith molecule by r;, and define the function f(r) by
When we insert (2.8) for the fourth, fifth, and sixth
factors in the integrand of (2.6) and integrate over )oo,
)oo, and )o4, and use (2.9) and (2. 10), then
r&o
o. (r(go. Do= o~ol, " q
9/2
Xf(lro r4I)f(l r~l)f(l r~ r~l)dr, dr, dr4dr4, (2.5) I(ai, a2, ao, a4, ao, ao)
e)de
(1+f)'(Sf)'[I(1,1, 1; 2, 2, 2)+3I(1,2, 2; 2, 1, 1)
L2~) J +6I(2, 1,1; 2, 1,2)+6I(1,2, 2; 1,2, 1)
i. .
" +3I(2, 1,1; 1,2, 2)+I(2, 2, 2; 1,1, 1)]
(2) / sintp
+3(1+f)'(Sf)'[I(1,2, 2; 1,2, 2)+2I(1,2, 2; 2, 1,2)
ph(p) dp, (2 7)
i , +I(2, 2, 2; 2, 1, 1)+I(2,1,1; 2, 2, 2) )
/'1'I
3(1+f) (8f)'[ I(2, 2, 2; 1,2, 2)+I(1,2, 2; 2,2, 2)]
h(p)=I(foal)=l I
)
v(ltf) exp(it ).)dt + (Sf)'I(2, 2, 2; 2,2, 2) }. (2. 14)
The polar coordinates of t, t', t" are denoted by
t'2)
(~) ,
' /'"
tv(t)
sinpt
p
dt. (2.8)
t, n,P; t', n', P', t", n", P", respectively, and their solid
angle elements are denoted by dQ, dQ', and dQ",
respectively (dQ=sinndndP). Now we use the addition
FOURTH VI RIAL COEFFICIENT FOR SQUARE FAVELL POTENTIAL 1419
theorem of the Bessel function to decompose We substitute this into (2. 18):
vo(a 'I),
I
~ n=0 m=O
00 00
(-;+I)(-', +m)(-,'+u)
f " J;(a t)
l m n
where b=3mo' is four times the volume of the hard Applying the Fourier transformation to the fourth and
sphere. The 6rst term inside the square bracket is the fifth factors in the integrand, we have
value for the hard sphere and its value cited by Riddell
and Uhlenbeck" is 1.2728. The accuracy of each term Pi 1' t'
in (2.24) can be estimated from Table II in the Appen- h(p )h(p )h(p )v(t)v(t')
dix. [By adding more terms for (t,m, n) to Table II,
(g) J J
we can make the coeKcient of (2.24) as accurate as Xexp(i[t (ps
y4)+t' (p&
ys)7)dp&dg&dy4dtdt'. (4.2)
we desire. ] Integrating over y2 and g4, we have
3. CALCULATION OF Dz
f
so ~' ' '
r
p'dp '
l
(1+f)~ (&)
p
This is the result obtained by Montroll and Mayer. '2
Inserting (2.9) for y(t), we have p2 l" ( J;(t)
+f PdP l (1+f)
Di= s'(327r')O' P (1+f)"'(Sf)"'(aiasasa4) &o
(2t)l
) ' sintp
]
l
p
tdh (4.5)
P means the summation for all 16 cases where ai, as,
a~, and a4 take the values 1 and 2, i.e.,
= 4s32o'~4 (1+f)'W **(1,1,p)
Di
pdp ~
-', (32s4) a'[(1+f)4W~,
;, *;4(1,1,1)11) 0
4(1+f)'Sf2='W;, ;, ;, *4(1,, 1)1)2)
16
+
(1+f)'(Sf)' 'W-:. :.:, 1, , ) (, (1+f)fW-:, :. (1,2,P)
4(1+f) (Sf)'2 'l'W * ~,*'(1,2,2, 2) 2
+
(8f)'2 'W. ;;
a'(2, 2, 2, 2) 7. (3.4) 2 p2
The necessary W;, **,, ,*(a&,a&, as, a4) values are given in +Sf'W:, -*.
,
l'*(2, 2,P) +f PdPL 7', (4 6)
Appendixes II and III. Using these values, we have i
Di/b' = (1/560) [544 4075f+ 35 007f' where the content of the second square bracket is the
99 687f'+139 215f47. (3.5) same as that in the first. W,*, ;, tl(ai, as, p) is given in
The first term, 544/560, is the value for hard spheres
Appendix IV for the cases where a, and 2. From =i
this we have"
and has been given by Rushbrooke and Scoins. '
= (1/4480) [6347+ 27 369f 156f'
Ds 'o'
, .
4. CALCULATION OF
h(p2)h(ps) h
(p4) h( l
D2
ys
pg l )
D&/h'
+594 272f' 1 518 980f4+918 540f'7 (4.
The first term, 6347/4480= 1.41670, is the value for
184
7).
Xh(I es es l)desdesde4 (4 1) hard spheres and agrees with the value of Rushbrooke
and Scoins. 8
"R. J. Riddell and G. E. Uhlenbeck, J. Chem. Phys. 21, 2056
'8 K. Hiroike has informed the author that he has obtained the
(1953).
"E. W. Montroll and I. E. Mayer, J. Chem. Phys. 9, 626 same results as (3.5) and (4.7) for Di and D2 independently
(1941). (private communication).
FOURTH VIRIAL COEFFICIENT FOR SQUARE WELL POTENTIAL 1421
X
values.
The value of D for the hard sphere obtained by
-10
Boltzmann' and by Majumdar4 is'4
0.288. E/b'
and that obtained by HappeP is is the
Rosenbluth~ "
value for the hard sphere obtained by Rosenbluth and
using the Monte Carlo method.
The temperature dependence of D~, D2, D3, and D is
shown in Fig. 3. As the unit of temperature we choose
the Boyle temperature T&, at which the second virial
-0.9715 coefficient vanishes. Above the Boyle temperature D&,
D2, and D3 are approximately constant and approach
the values for the hard sphere, and the first and the
third are negative while the second is positive. Their
absolute values are of the same order of magnitude and
the contributions to D from these three cancel for the
1.4167 most part. Below the Boyle temperature each of them
becomes negative and approaches negative infinity as
D2 T tends to zero, being of the order of e "~' e T "I'
2
I
3
I
and |, "I~, respectively. Such a feature of the temper-
ature dependence of the fourth virial coeKcient and its
components will also occur in the case of the Lennard-
Jones potential.
~-0.1589 In general, the eth virial coefFicient tends to ~00
D3 &n(n 1) e/2kT 2n(n 1) Hence g& g& D & D
and D3x" for x = e ""r (f=x ' 1) are sho
wn in Fig.
4. Figure 4 shows the contribution of each component
0. 5 of D to the total D, especially at low temperatures.
The D3 contribution is the main part at low tempera-
tures. Such a contribution of D3 to D makes us suggest
that the summation of the ring approximation" of
irreducible cluster integrals, which is equivalent to the
solution of Green's linearized integral equation, is not
FIG. 3. Temperature dependence of D1, D2, D3, and D. The unit
of temperature is the Hoyle temperature. a good approximation over the whole temperature
region. For example, it can be proved that the isotherm
"Boltzmann and Majumdar used the result by Van Laar
I Archives du Musee Joyler ser. 2, 6, p. 237 (i900) =Amsterdam '5M. N. Rosenbluth and A. W. Rosenbluth, J. Chem. Phys.
Alrad. Versl. Jan (1899), p. 350j. 22, 88i (1954).
1422 SH I GETOSH I KATSURA
FIG. 5. Normalized
second, third, and fourth
cluster integrals for the
square well potential.
b4* was calculated using
the value of D in the
present result. This fig-
ure was calculated by
T. Kihara.
obtained from the ring approximation for the square tive comparison, however, wil] depend on the precise
form of the potential.
well
obtained by Rodriguez. "
potential has a singularity similar to the one
The origin of such a singu- The discussions of the distribution-function' "
larity in this isotherm may be attributed to the neglect method often use the comparison of the true D and
of other irreducible graphs. As a criterion of the validity approximate D. One should, correctly, use the compari-
of the ring approximation and similar ones, one should son over the whole temperature range, rather than only
show that the isotherm behaves well at low tempera- the value for hard spheres.
tures. The method of Sec. 2 of the present paper can be
In the case of the lattice gas' the alternative signs applied to D~, giving the result
of the virial coefficients appear. In the present results,
D2 = ' (64m. 4) 0'
8, C, and D are negative at low temperatures. It is an ,
at o ~ ~
a5
interesting question whether the higher virial coeffi- n1+m2 =5
cients E, F, . . . at low temperatures are all negative
at ay=i or 2
TABLE I. Correction of the critical data of zeroth approximation by Kihara' due to the fourth virial coe%cient D.
The third line indicates the comparison of the various temperature variables, e/kT, T/T~, f, and g.
Pb/kTa pv/kT
Zeroth approx. (from 8 and C), Kihara 0.06656 1.9184 0.3333 0.3485 0.3831 0.41688 0.8403
First approx. (from 8, C, and D), present results 0.04865 2. 6086 0.3629 0.3819 0.3497 0.4654 0.8261
Hoyle temp. 0.13353 1. 0, 14285 0.9351
& See ref'erence 5.
F 0 IS R T H VI RIAL C 0EFFI CI EN T F0R SQ UA RE KV ELL P0TFN TIA L 1423
&
2vri gives
1 1 p
ay-"+'1 r pay"
(A. 1) = b'I ! [
dsl
2 Qn- &2b) 27ri~ z, (2bl
I(-s)l'I ( -s+-
2 (
1
23
- -2j
( -s+1- -l q i~l p s+ 3+m+n+l
l q
l~l
2 )! &
~
(A.3)
m+n 1+2) |' m+n i+5) ( m+n 1+2)
Ii'I s+
l~l -+ ) & 2 )
Since a/2b&1 for a, b=1 or 2, the integration can be the integrand, and only s=0 remains for m=e, and no
obtained from the residue of the poles in the right plane pole remains for n&m The p. oles of I'( s+2) cancel
of L those of the third factor of the denominator and
The necessary integral can be confined to the case s=~i, 3~, -+
3~2m+-', nremain. The poles of I'( s+1)
where m and e are both even or odd and e(m with cancel those of the fourth factor of the denominator and
l=0, and to the case where l and m are both even or s=1, 2. . .-', m n remain for m&n+2, and no pole
',
t
m+n+3q
1(l)1
)
I
2
(A. 1) = al
4(2~) l m+n) mn)
r ( 1+
(m+n+5q
I(-:)Il 1+
l, o, l; (a/2b)' I+
2 2 2 2
;
j ( m n+1 ) (m n+1$
r(3)rl irl
j 2 ) I
(m+n+4 m n+1 m n
2 +n+1
m
x4Fai ; ', -'3; (a/2b)'
,
I
2 2 2 2
I ( 1)I'( :)I
]m+n+5 y )a p '
l
2 j (2bj
m+ny )m +n+3y pm ny
r(-,')r Ir il'
) &2)
m+n+5 m n+2 m n 1 m+n+2
x4pal
I
; 2, ';
-'-, (a/2b)' . (A.4)
2 2 2 2 ) I
SH I GEYOSH I KAYSURA
2&E
Q(111)
p(111)
Epp(112) =0
242/96
Epp(122)
31/7680
Epp(121)
0
Epp (122)
z2Q(212)
Epp(122)
EQ4 E4p(111) E4p(211) =0 E4p(122) 2', (111)
o E4p(112) = 0 Epp(122) Epp(121) Epp(212)
Egg 53/480 0 1503/5120 2&Eu (111) 242/30 709/7680 Egg(121) EII (212)
Epp 35/6912 0 10251/131072 2&Epp (111) 2@2/216 3883/442368 Epp (121) Z(212)
Egp 17/960 0 1257/40960 2VCI3(111) 0 333/20480 2v2/30 77/15360
En Erp(111) E&p(211) =0 Egp (111) 2&Egp (111) Egp (112) Eip(221) E,p(121) =0 Egp(212)
In the above 4Fs(nr, np, np, n4, pq, ps, pp, x), when the over dt (Weber-Schafheitlin's integral), we have
number of n; which are equal to zero is larger than that
of P, which are equal to zero, &Fp1. When there exists =
1/r (zero or negative integer) in the constant factor,
this term is put to be equal to zero. 1
The integral in the latter case (v=0, t and m are X (A. S)
both even or odd) can be obtained in the similar way. ', ) s (s
(s+3) (s+ 2) (s+ ') (s
', ) ,
The summation for m is replaced by the integral (0~ p~2). (A. 11)
representation with the residue of r( s), We express the Bessel function J(t) by the product
1 1 ~ r ( s)r (s+2) a'+" of the exponential function and the polynomial:
!."
4$-
2~i +~~, i (2)p (1+-iq
:. '(12t)=
r(s+-,')r(s+4) 1
lid-. , *.
F '
e"I
16 Epr)
I l
(2p)'* & 4 t)
I
where I' means the principal value. Let it=s; then values of the above integrals are given by the integrals
over a semicircle of in6nitely small radius, i.e. , J~/2 (8
WI I., I*'(1,2, p)
and J'/2 "d0, respectively. When we expand the
integrand in Laurent series beginning from s ', the
1
1+
I' 1
+I' ds s-'e&'+&'I FIG. 6. Integration
2s 2s') paths in (A. 14).
+I'
/"
dss 'e~ '+&'I ( 1
1
1)
2s 2s'i
{a) {b)
+I'
3
'+'~'I ( 1+
1)-
dss 'e& + 2s')
I (A 13)
coeKcients of the negative even powers of s do not
2s
appear and the integrals of the negative odd powers of
s vanish since
In each of the above four integrals the pole of the
integrand is only s=0. The third integral for p~1 and
the first and the second integrals vanish when they are 2n lgs
integrated over the left half-circle and imaginary axis e 2nqd + 0
indented the origin LFig. 6(a)]. The third integral for
p&1 and the fourth integral vanish when they are
integrated over the right half-circle and the imaginary Therefore the terms contributing to the integrals are
axis indented the origin Fig. 6(b)]. Hence the principal
I only the terms of order s '. We pick up these terms; then
where C and C2 are the semicircles around the origin more suitable. The results are
with in6nitely small radius, /23
2
and J'/2 J'
respectively. W;;, ,*'(a,a, p)
Hence we have
W*, , (1,2,p)
Vp
I
-+ I,
(4p 1 (pt')
(3 a 12 (a) ) I I
0~ p&2a. (A. 17)
2(2m)&
1 1 1
30p'+72p 27), 1~p~ 2, =0) 2a~ p.
(p4 (A. 15)
96 +~ Qp
APPENDIX IV
W.; ,*. ;, '(1, 1,p) and W;, I *, '(2, 2,p) can be integrated by A method similar to that of Appendix III can be
this method. The method of Appendix II, however, is applied and gives
SH I GETOSH I KATSURA
8! ( 7! ( a)
I
4~ ga 9! a a)
I
a) 5!
(1+a)' 1 (1+a)' ( 1) (1+a)' ( 1) (1+a)' ( 1) (1+a)'
-+ 1+- I+ -1+- I+ -1--I+
7! ( 6! (
I I
9!, a 8! a~ & aJ a&
I
5!
(u
-+, -1+-1) (a 1)' ( 1)I+ (a 1)' t' 1)I+ (a 1)'
1)' 1 (a 1)'!
I+, -1-- I1--
6! ( a)
I
8! (
I
9! a aP 7! ( gJ 5!
(g 3)' 1 (g 3)' (
3) (a 3)'
3) (a 3)' ( 1) (a 3)'
9! g
-+ 1
8! & a)
I+ (3
I
7! E a)
-I
6! 4 a~
3 I+
5!
I I+, (A. 19)
The double sign before the third L ) should be taken as + for a~1 and ss for g~1.
1 1 625i V2 92051
;
W.~~;, (2, 1, 1, 1) = IV.;, ;, 1, ;4 (1,2, 2, 2) = 8W;, ;, ;, ;4(-,', 1, 1, 1) = (A. 20)
v2 m 2'X2835 ~ 2835X2
PIC YSI CAL REVI EW VOLLJM E 115, NUM B ER 6 SEPTEMBER 15, 1959
As optical aggregation of F centers proceeds in KI the E, M, and E bands develop, but later lose their
identity in a very broad band, which is absent in KCl and KBr. The shape and position of this band are
temperature independent, and it is removed from the peak of the true colloid band. A new band on the
short-wave]ength side of the F band was observed in crystals containing high concentrations of F centers.