1898 T. G. SLANGER AND G.

BLACK
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Chem. Phys. 51, 116 (1969).
18 T. G. Slanger and G. Black, J. Chem. Phys. 51, 4534 (1969).
19 E. C. Y. Inn (private communication).
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THE JOURNAL OF CHEMICAL PHYSICS
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VOLUME 54, NUMBER 5 1 MARCH 1971
Enskog Theory for a Rigid Disk Fluid*
DAVID M. GAsst
Lawrence Radiation Laboratory, University of California, Livermore, California 94550
(Received 3 August 1970)
The Enskog theory for a dense fluid of rigid disks is developed. The collisional contribution, which
dominates in liquids, is derived and added to the kinetic term, which describes a dilute gas. Expressions
for shear and bulk viscosity and for thermal conductivity are obtained. The initial correlations are evaluated
via the autocorrelation function approach, and the exponentially decaying functions which result are
related to the Enskog theory.
I. INTRODUCTION
Calculations in two-dimensional systems often serve
as prototypes. In the investigation of long-time correla-
tions by molecular dynamics computation, rigid disk
systems are within the practical limitations of present
day computers, whereas hard sphere systems are not.!
The density expansion of the transport coefficients,
based upon a generalized Boltzmann equation for a
two-dimensional system, breaks down in the triple colli-
sion contribution, affecting the first-order density cor-
rection.' In three dimensions the density expansion
breaks down beyond first order in the density, thereby
complicating the numerical evaluation of the diver-
gence. The Enskog theory for rigid disks can be used
as a handle on these and other rigorous calculations.
The Enskog theory for a hard sphere fluid
3
yields
transport coefficients over the entire density range and,
in the low density limit, goes over to the Boltzmann
form. The Enskog theory takes into account exactly
the term in the Boltzmann equation which arises from
the difference in position of colliding molecules. In
addition, the influence of triple and higher-order colli-
sions is approximated by scaling the Boltzmann collision
integral with the local equilibrium radial distribution
function at contact. The same observations also apply
to a rigid disk fluid. The kinetic contribution to the
transport coefficients of a rigid disk fluid has been ob-
tained by Sengers.2 This contribution arises from the
bodily movement of molecules between collisions. In
dense fluids the collisional or potential contribution is
dominant. This term, which derives from transport
between molecules while they are in contact, is the one
on which we focus in this paper.
In the Enskog theory, correlations in time among
many molecules are only estimated, while two-body
effects are calculated exactly. Correlations for short
times, as reflected in the various autocorrelation func-
tions, are expected to be more accurately described by
this theory than those which persist for many mean
collision times. This observation is important since
hydrodynamic and molecular dynamics calculations
4
suggest a slow decay for the autocorrelation functions,
while exponentially decaying functions result from the
low-density, zeroth-order Sonine polynomial solution
to the Boltzmann equation. As yet, only the velocity
autocorrelation function has been shown to possess a
long-time tai1.
4
However, since the stress and heat-flux
autocorrelation functions contain a term which depends
only on the velocity field at long times, it is reasonable
to suppose that these functions decay slowly at such
times.
The initial values and slopes of the autocorrelation
functions are evaluated. Then the assumption of expo-
nential decay yields transport coefficients which agree
with the ones calculated from the low-density, zeroth-
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ENSKOG THEORY FOR A RIGID DISK FLUID 1899
order Sonine polynomial solution to the Boltzmann
equation. Initial correlations are related to terms which
appear in the Enskog theory.
II. COLLISIONAL TRANSFER
In as much as the Enskog theory for dilute systems of
rigid disks is already known,2.5 only the collisional con-
tribution is required in order to evaluate the transport
coefficients for dense fluids. This term arises from the
instantaneous transfer of a molecular property across
a line, I, while two disks centered on opposite sides of
t are in contact.
Use of the molecular chaos approximation implies
that the probable number of collisions per unit time,
where c, CI, and k lie in the ranges dc, dCI, and dk, is
(uk) (uk) ]u
2
(gk)dkdcdcI(kn)dl;
(1)
c and CI are the velocities of the colliding molecules, k
is a unit vector in the direction of the line of centers,
x(r) is the Enskog scaling factor, f is the one-particle
distribution function, (uk) and (uk) are the
centers of the two molecules of diameter u, g= CI- c,
and n is the unit normal to t.
For each molecular property, if;, at each collision,
there is a net transfer of if;' -if; across I, where if; is the
value prior to collision and if;' is the value after colli-
sion. The total rate of transfer across I by all collisions,
per unit length, is
1fl (if;' (uk) (uk)]
gk>O
X (gk) (kn)dkdcdcl. (2)
The above expression, which is of the form Vrn, gives
the vector flux, V" of if;. Inasmuch as only linear trans-
port coefficients are of interest here, the distribution
functions in (2) can be expanded about the point of
contact of the disks, r, and only terms up to the linear
term in the gradien t are kept. Linearization yields the
collisional contribution to the flux
V,=I+i{ilx)J f fW-if;)fORk
. (a/ar) log(j/R) (gk)kdkdcdcI, (3)
where
fO is the local equilibrium single-particle distribution
function, and all quantities are evaluated at r.
III. MOMENTUM TRANSPORT
In order to evaluate the momentum transport, we
take if;=mC=m(c-co), where Co is the macroscopic
velocity at the point r. Substitution of if; into Eq. (3)
and integration with respect to k using the identities
(5) and (6) yieldEq. (7):
f(C'-C)k(gk)dk= Jkk(gk)2dk= t1l'(2gg+g2U),
(5)
Jkk(k V) (kg)2dk= (4/15)
X[V.g(gg+g2U)/g+g(Vg+gV)], (6)
where U is the unit tensor and V denotes a vector,
which will be taken as (a/ar) log(j/R):
V m = ft (1I'
mu2
x) ff fh (2gg+ U g2) dcdcI
(
a fO a fO)]
+ g g - log - + - log -0 g dcdcl.
ar R ar h
(7)
Since g= C
I
- C and the odd moments of C and C
I
are zero, and since Jfdc=N / A=nand ffCCdc=n[CC]I,
the first term in Eq. (7) can be written as
V
m
l=i{bp
2
x) (2[CC]I+[C2]IU), (8)
where the coarea, bp=H1I'nu
2
), and p=mn have been
introduced. The remaining term in Eq. (7), V m
2
, con-
tains the factor
(9)
The terms involving aT/ar in V
m
2 are odd functions of
C or CI and thus vanish on integration. The remaining
terms are more conveniently evaluated when the vari-
ables G
o
= (C+C
I
)/2 and g=CI-C are introduced.
The result is
V
m
2= - (2::TY ff exp [- (
G
0
2+tg2)]
X {aco : gg(gg+g2U)
ar g
+g .g) g+g .g)]} dGodg. (10)
Performing the integration indicated in Eq. (10)
yields
Vm2= -wIHaO[co]/ar)+Hl(a/ar) co), (11)
where w= (5n2ilx/8) (1I'mkT) 1/2 and
aO[coJii /ar= acdar
j
) + (acoj/ari) (a/ar) . COOij.
The sum of Eqs. (8) and (11) yields the collisional
contribution to the momentum flux and is the potential
part of the pressure tensor. The rate of transport due
to molecular motion between collisions is p[CCJ. There-
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1900 DAVID M. GASS
fore, the total pressure tensor is
F= p[l (bpx) J[CCJ+i (bp
2
x) [C2JU
-wi t(aO[coJ/ar) +tU(a/ar) col. (12)
To first order in the gradient,
p[CCJ = nkTU -x-
l
[l (bpx) J21)0(a
O
[coJ/ar), (13)
where 1)0= (1/20') (mkT/Tr)
I/2
b
o
(N) is the coefficient of
shear viscosity of the dilute gas. Further, the hydro-
static pressure, PO, is given by
P=knT(1+bpx) - (4w/5) (a/ar) co. (14)
The deviation of the pressure tensor from the hydro-
static pressure, from Eqs. (12)-(14) and the identity
[C2J=2kT/m is found to be
tlF= -I (21)0/x)[1+Hbpx)J2+twl (aO[coJ/ar). (15)
The definitions of wand 1)0 are used, and the identifica-
tion of the coefficient of -2(a
O
[coJ/ar) with the co-
efficient of shear viscosity yields
1)= 1)obp(l/bpx) + 1 + bpx Ii+ [2/Trb
o
(N) Jl). (16)
The third Sonine polynomial approximationS gives
b
o
(3) = 1.022 and therefore
1) = 1)obp[ (l/bpx) + 1 +0.8729bpx]. (17)
Vm2 depends on only the local equilibrium distribution
function and therefore does not depend on the Sonine
polynomial correction factor, bo(N).
The coefficient of bulk viscosity, c/J, is identified with
the coefficient of - (a/ar) coO in Eq. (12) and there-
fore
c/J= 4w/5 = [4x/ll'bo(iV) J (bp )21)0, (18)
which becomes
c/J = 1)
o
bp (1.246bpx) ,
when b
o
(3) = 1.022 is used.
s
IV. ENERGY TRANSPORT
(19)
In order to evaluate the energy transport, we take
1/I=mC2/2. Integration with respect to k in Eq. (3)
using Eqs. (20)-(22) yields Eq. (23), which is the
collisional contribution to the heat flux:
J (C
'
LC2)k(gk)dk= Jk (g+2C)k(gk)2dk
=2J(kG
o
)k(g.k)2dk, (20)
2J (k Go)k(gk) 2dk= ill'[2g(g Go) + g2G
o
J, (21)
J (C
'
2-C2) (k V) (gk)kdk
= !s{ Go g[g(g. V) +g2VJ/ g
+g[g(Go V) +Go(g V) Jl, (22)
Ve= /6 (ll'
mO'2
X) J Jffl[2g(g Go) + g2G
o
Jdcdcl
+ /5 (mO'3X)J JjOR[ (Go g) (gg+g2U) /g
+g(gGo+Gog)]- VdcdcI, (23)
where V= (ajar) log(f/R). As 2g(gG
O
)+g2G
O
=
![C
I
2C
I
+C2CJ, the first term in Eq. (23) is
(24)
Use of (9), where now the terms involving aco/ar
are the integrals of odd functions of C and C
I
, and the
introduction of the variables Go and g yield
+g(g.G
o
) (gGo+Gog). aT] dGodg. (25)
ar
Integration over Go and then g yields
(26)
where C
v
= kim and w= (uSn2x) (ll'mkT)I/2.
The collisional contribution of the heat flux, given
by Eqs. (23), (24), and (26), is augmented by the
energy transfer due to molecular motion, (p/2) [C2CJ,
and the total energy flux, Q, is thus found to be
Q= + (3bpx/4) J[C2CJ-c
v
w(aT /ar). (27)
To first order in the temperature gradient,
= - [1 + (3bpx/4) J(Ao/x)(aT /ar) , (28)
where Ao= (2/0') (k
3
T/mll')I/2al (N) is the low-density
formulation of the coefficient of thermal conductivity.
The insertion of (28) into (27) yields
Q= - ['\o/X[l+ (3bpx/4) J2+cvwJ(aT /ar) , (29)
and thereby the coefficient of thermal conductivity, A,
can be expressed as
A = (AD/X) [1 + (3bpx/4) J2+cvW
= Aobp(l/bpx) +!+bpx{ 1
9
6 + [l/ll'al (N) Jl). (30)
The third Sonine polynomial approximationS gives
al(3) = 1.029 and therefore
A= Aobp[ (l/bpx) +!+0.8718bpx]. (31)
V. AUTOCORRELATION FUNCTIONS
At low densities exponentially decaying autocorrela-
tion functions lead to coefficients of shear viscosity
and thermal conductivity equal to the ones calculated
from the zeroth-order Sonine polynomial solution to
the Boltzmann equation. This result was first observed
for the shear viscosity in rigid sphere systems.
6
We next consider the shear and bulk viscosity in
some detail. The presentation is based on that of Ref.
6. The coefficient of shear viscosity, 1), for long-wave-
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ENSKOG THEORY FOR A RIGID DISK FLUID 1901
length, zero-frequency processes is given by
71= (AkT)-ll'" (jXy(t)jXy(t+r) )dr
o
I
t
J'" = (AkTts)-l jXy(t)dt jXY(s)ds,
o t
(32)
where ergodic theory considerations and a variable
change from t+r to s allow the passage to the second
formulation of Eq. (32), and where
N N
JXY(t) = m L Ci""(t)Ciy(t) + L Rix(t)Fiy(t)
i=l i=l
N
= m L Cix(t) Ciy(t)
i=l
m
+"2?;j uki/kil(kij"gij)O(t-te), (33)
Cix(t) and Ciy(t) are the x and y velocity components of
particle i at time t and Fiy(t) is the y component of the
force on i at time t. The direction of the line of centers
from j to i is given by kij and the relative velocity
gij=Cj-Ci' The second formulation of Eq. (33) is a
specialization to rigid disk systems where te is the time
of collision c. The zeroth-order Sonine polynomial solu-
tion of the Boltzmann equation for the coefficient of
W(O), 5(0), and (Rc
xY
)2> can be evaluated exactly:
shear viscosity yields
7Joo=7Jo/bo(N) = (1/2u) (mkT/rr) 1/2,
and the Enskog expression for the collision rate of rigid
disks is r= (2Nbpx/u) (kT/rrm) 1/2. With the help of
these expressions Eq. (32) can be converted into
71 [srl'" - = X-I - W(t)dt
710 N 0
(34)
The effects of considering rigid disks, as compared to
hard spheres, are included in the coefficients of the
integrals of Eq. (34), which can be compared to Eq.
(S) of Ref. 6. The definitions of W, 5, and R/Y are
given in Eq. (7) of this reference.
'"
(Re
XY
)2) and L (RexYRe+kXY)
k-l
arise from correlations of molecular forces. The former
term is a zero-time correlation effect and represents
the contribution of instantaneous correlations to the
transport coefficient.
m2 N
W(O)= 4N(kT)2E (c/c/)=t,
(35)
(
m )3/2 J J J dcdc1dk exp[ - (m/2kT) (C
2
+CI
2
) ] (gk)2kXkY(cXCY+ClxCIY)
5(0) = - 2kT J J J dcdc
1
dk exp[ - (m/2kT) (C
2
+CI
2
) ](gk) .
(36)
First, the coordinate transformations, c_= C-Cl and C+= C+Cl, are made and the integrations over C+ are carried
out. Next k is projected onto L and a vector orthogonal to it, CJ.:
k=(L/i Li) coso+(cJ./i cJ.i) sinO, (37)
where 0 measures the angle between c_ and k. The expression of k
x
and k
y
in terms of 0 using (37) and the use of
the identity (gk)2= (cOS
2
0)C
2
allow the integrations in (36) to be carried out with the result
5(0) = - (1r)1/2/SV2,
(Re
xY
)2)= ~ ) J J J dcdc1dk exp[ - (m/2kT) (C
2
+CI
2
) ](gk)3(kXkY)2
2kT If J dcdc
1
dk exp[ - (m/2kT) (C
2
+CI
2
) ](gk)
_lc
-4'
The contribution of the (Re
XY
)2) term to 71 is given by Eqs. (39) and (34), and is
71(0) = 7Jobp[2bpx/1rbo(N)],
(3S)
(39)
(40)
where the zero in the parentheses indicates it is the zero-time contribution. 71(0) is identical to the unperturbed
single-particle distribution function's contribution in the Enskog theory.
The initial slope of Wet) can be calculated exactly and that of Set) can be calculated using the molecular
chaos approximation. It is then found that both decay as e-', where s is the mean number of collisions per particle.
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1902 DAVID M. GASS
The diagonal elements of the stress autocorrelation function characterize the coefficient of bulk viscosity, :
+1)= (AkT)-! [" (Jq,XX (O)Jq,xx (t) )dt,
o
(41)
where Jq,xx(t) =Jxx(t) - (px(t, with pI given by (33) when x replaces y, leads directly to
P+1)P= 1)
0
0 [16 (b
pX
)2 o (Rc
xx
)2)+ f (R/xRc+kXX].
X 7r k=!
(42)
Only the term involving intermolecular forces in px has been written in Eq. (42), as it is the only nonzero con-
tribution to in the Enskog theory. Further,
(
)2
(
m )fffdCdCldkexp[-(m/2kT)(C2+C!2)](gok)kX4
Rxx )- -
c - 2kT f f fdcdc!dk exp[ - (m/2kT) (C
2
+CI
2
) ](gok)
=1
(43)
A comparison of Eq. (18) with Eqs. (42) and (43) indicates that the only contribution to the bulk viscosity in
the Enskog theory arises from zero-time correlations of the diagonal elements of the stress tensor. The only non-
zero contribution to from the initial autocorrelation of the microscopic stress tensor is due to the correlation
of the impulsive force term with itself at the time of collision of two molecules. Evidently the deviations from
local equilibrium (in the distribution approach) give rise to correlations of more than two particles and to cor-
relations separated in time.
Similar calculations can be performed for the coefficient of thermal conductivity. The results again show an
agreement between an exponentially decaying autocorrelation function and the zeroth-order Sonine polynomial
solution to the Boltzmann equation. For the heat flux autocorrelation function the decay is found to be ~ e / 2 .
VI. DISCUSSION
This paper presents the Enskog theory for a dense
fluid composed of rigid disks. The collisional contribu-
tion, which dominates in dense fluids, is derived and
added to the low-density kinetic term. By determining
the initial values of the autocorrelation functions, we
conclude that, at low density, an exponential decay of
the microscopic stress tensor and microscopic heat flux
autocorrelation functions gives results identical to the
zeroth-order Sonine polynomial solution to the Boltz-
mann equation. The exponent of the decay agrees with
that found for the cross term (which is first order in
the density) under the molecular chaos approximation.
The collisional contribution to 1) and to A contains
one term dependen t upon the single-particle equilib-
rium distribution function and one term dependent
upon deviations from this distribution. The former
term, which is more than twice the latter for 1) and
more than half the latter for A, is equal to the contribu-
tion of the instantaneous correlations of the stress
tensor and heat flux to the transport coefficients. Thus,
the integration of the exact autocorrelation functions
from time zero to a few mean collisions times, when e-
S
and e-
s
/
2
are essentially zero, should give transport co-
efficients not unlike those predicted by the Enskog
theory. The early time behavior of Wet) and S(t) is
not expected to be greatly dependent on the density,
whereas
(Rc i.iRc+! i.i)
might vary by a factor of 2 over the fluid density range,
as it does in systems of hard spheres.!
At long times in rigid disk systems, correlations are
not believed to decay rapidly. This discrepancy from
the Enskog theory reflects the approximate treatment
of multiple correlations by the scaling of two-body
interactions. It is hoped, however, that the Enskog
theory, which represents the "best" scaled, binary colli-
sion theory, might be grafted onto a realistic long-time
description, involving a hydrodynamic model. The
availability of such a theory will provide the means
for the accurate determination of transport coefficients
for rigid disk systems.
ACKNOWLEDGMENTS
The author would like to express his appreciation to
T. E. Wainwright, W. G. Hoover, and B. J. Alder for
helpful discussions.
* Work performed under the auspices of the U.S. Atomic
Energy Commission.
t Present address: Physics Dept., University of Toronto,
Toronto 5, Ontario, Canada.
1 B. J. Alder, D. M. Gass, and T. E. Wainwright, ]. Chem.
Phys. 53, 3813 (1970).
2]. V. Sengers, in Lectures in Theoretical Physics, Kinetic
Theory, edited by W. Brittin (Gordon and Breach, New York,
1967), Vol. IXC, p. 335.
3 S. Chapman and T. G. Cowling, The klatlzematical Theory of
Non-Uniform Gases (Cambridge U. P., London, 1939). The
notation of this reference is used throughout this paper.
4 B. J. Alder and T. E. \Vainwright, Phys. Rev. 1, A18 (1970).
5 ]. V. Sengers, "Triple Collision Effects in the Thermal Con-
ductivity and Viscosity of Moderately Dense Gases," Arnold
Engineering Development Center, Tenn., 1969, Tech. Rept.
AEDC-TR-69-68.
6 T. Wainwright, J. Chem. Phys. 40,2932 (1964).
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