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Complete binary collision approximation for the gas transport coefficients via
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JOURNAL OF CHEMICAL PHYSICS VOLUME 109, NUMBER 9 1 SEPTEMBER 1998

Complete binary collision approximation for the gas transport coefficients

via the time correlation formulation
Saman Alavi and R. F. Snider
Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada V6T 1Z1
~Received 10 April 1998; accepted 29 May 1998!
The connection between the low density limit of the time correlation equations for the transport
coefficients and the solution of the Boltzmann equation to lowest order approximation appear to
have been made in essentially two different ways. Either the time correlation function is evaluated
by using the time dependent ~linearized! Boltzmann equation, or by utilizing a resummation of an
expansion in the reciprocal of a convergence parameter. As well, the connection is often made to
only the lowest order solution of the Boltzmann equation, ignoring the possible importance of
higher order moments ~Sonine polynomials! in the solution of the Boltzmann equation. The present
work uses a projection operator method and a subsequent binary collision expansion of the time
correlation function to retain all contributions to the transport coefficient from binary collisions.
This explicitly avoids an expansion in a divergent parameter and reproduces all Sonine polynomial
contributions to the transport coefficient. Gas transport coefficients for a binary mixture are obtained
in a similar manner. © 1998 American Institute of Physics. @S0021-9606~98!51333-5#

I. INTRODUCTION correlation function is a double dot contraction. In most of

1 2
the literature it is standard to use the tensorial components,
Since the pioneering work of Green and Kubo, the dy- thus for the shear viscosity, h , the thermal average is typi-
namic evolution of many systems has been expressed in cally seen as
terms of time correlation functions. For an N-particle system,
a time correlation function has the general form

1 a 1 a
h 5 lim lim
e →0 1 N,V→`
i
2kTV K
Ixy
1
I
i e 2L xy
. L ~3!
C~ t ! 5 ^^ I( I~ t ! && 5 ^^ I( e 2itLI&& , ~1! N/V5const.
2 a 11 2 a 11
where I is a tensor valued phase space function of rank a Since Ixy is one component of a second rank symmetric
belonging to an irreducible representation of dimension traceless tensor, it belongs to the 5-dimensional irreducible
a representation of the rotation group. By the rotational invari-
2a11 of the 3-dimensional rotation group, ( represents an ance of L and of the thermal average, the quantity of Eq. ~3!
a-fold dot ~tensorial! contraction, L is the N-particle Liou- is 1/5th the sum over all traceless symmetric components,
ville operator and the bracket designates a thermal average which appears in Eq. ~2!. The advantage of expressing the
over the phase space of an N-particle system of volume V. transport coefficient in a rotationally invariant form is that
Time correlation functions have found application in many the rotational properties of the different operators can be
fields including light and inelastic neutron scattering, spec- used to simplify its evaluation.
troscopy, the theory of electrical conductance and in the cal- The original motivation for examining the time correla-
culation of thermal transport coefficients.3 tion function formulation of the transport coefficients was to
A transport coefficient s is the particular limiting form understand the density corrections to the dilute gas transport
of the Fourier transform of the time correlation function of coefficients, in particular to establish any relation to the vi-
the flux I of some property, specifically able computational method of Rainwater and Friend.4 The

s 5 lim lim
e →0 1 N,V→`
N/V5const.
iB
~ 2 a 11 ! V
K a
I(
1
i e 2L
I L . ~2!
latter theory is a composite of a number of developments,
whereas a derivation from a unified formalism would be de-
sirable. This would also require understanding the role that
bound states play in gas transport. As a closed equation for
Here B is a factor appropriate for each transport coefficient the transport coefficient, Eq. ~2! should be capable of evalu-
and the introduction of the volume factor V recognizes the ation without recourse to the Boltzmann equation, and in
extensivity of a flux and the intensivity of a transport coef- doing so, provide an independent approach to justify or con-
ficient. The flux may be a scalar ~bulk viscosity!, a vector tradict the density corrections obtained by the Boltzmann
~diffusion and thermal conductivity! or a second rank tensor equation and its generalizations. It appears that most pub-
~shear viscosity!. For diffusion and thermal conductivity, a lished comparisons between the time correlation function
is thus 1, so the tensorial contraction in the time correlation formulation and the results of the Boltzmann equation5–9
function reduces to a simple dot product, while for the shear evaluate the time correlation function using the Boltzmann
viscosity, a is 2 and the tensorial contraction in the time equation or some generalized kinetic equation. In contrast,

0021-9606/98/109(9)/3452/9/$15.00 3452 © 1998 American Institute of Physics

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J. Chem. Phys., Vol. 109, No. 9, 1 September 1998
Zwanzig10 uses a binary collision expansion to deduce that
the evaluation of Eq. ~2! requires the solution of a series of
integral equations, the lowest order of which is recognized as
the linearized Boltzmann equation. But in order to carry out
this procedure, Zwanzig had to resum an infinite series in
powers of 1/e whose individual terms formally diverge as
e→0. Kawasaki and Oppenheim11 have extended Zwanzig’s
method to obtain density corrections to the viscosity coeffi-
cient and make contact with the theory of Choh and
Uhlenbeck.12 The method presented here avoids the 1/e ex-
pansion by using another technique, also introduced by
Zwanzig,13 namely the use of projection operators.
While examining the density corrections to the dilute gas
transport coefficients, it was noticed that the standard treat-
ments that make connection between these disparate formu-
lations ~time correlation versus Boltzmann equation! appear
to focus on only the first moment approximation to the
Boltzmann equation and do not consider the derivation of
corrections associated with higher moments ~Sonine polyno-
mials! for the accurate calculation of dilute gas transport co-
efficients. It is the purpose of this paper to show how these
higher moments arise solely from the time correlation formu-
lation. Thus the applications presented are limited to gases at
low density to deduce expressions for the transport coeffi-
cients in terms of kinetic cross sections, while retaining all
binary collision effects. The same method of approach is
adapted to the inclusion of the necessary multiple moments
required for the calculation of the transport coefficients of
mixtures. The presentation for mixtures is limited to keeping
only one expansion term per species, but it is clear this could
be extended to all binary contributions. Many of the tech-
niques shown here will be used when expressions for the
density corrections to the transport coefficients are derived in
later work.
In Sec. II, projection operators are defined and used to
carry out a direct resolvent expansion of the time correlation
function for a transport coefficient, to derive a result similar
to that of Zwanzig.13 For dilute gases it is clear that a binary
collision expansion14 is needed at some point in this relation.
In Sec. III, I is assumed to be a sum of 1-particle functions,
and with the use of a binary collision expansion, an analytic
solution is obtained for the low density part of the transport
coefficient. In Sec. IV, this solution is interpreted as includ-
ing the complete set of Sonine polynomials. Section V rein-
terprets the formalism of Sec. III to derive an expression for
the transport coefficient of a system which is a mixture of
two species. In that case, for simplicity, only a single mo-
ment for each species is considered. The paper ends with a
discussion.
II. PROJECTION OPERATOR—RESOLVENT
RELATIONS
The thermal average bracket ^^u&& involves the ‘‘bra’’ and
‘‘ket’’ defined either in quantum or classical mechanics as
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S. Alavi and R. F. Snider 3453
^^ Xu [ E dxN X[Tr1•••N X,
1
u Y&& [Yf ~ N ! [ @ Y, r ~ N ! # 1
2
^^ Xu Y&& [ E 1
dxN XYf ~ N ! [ Tr1•••N X@ Y, r ~ N ! # 1 ,
2
~4!
where, if only translational degrees of freedom are involved,
a phase space element is dxN 5dpN drN , while in quantum
mechanics, the noncommutation of an observable Y and the
equilibrium density operator r (N) requires, for example, the
introduction of the anticommutator to preserve hermiticity.
Obvious generalizations are required if there are internal
states and/or the molecular system is a mixture. It is the
classical terminology and language that will be used here,
but the classical formalism can be immediately transcribed
into a quantum formalism. The bracket acts as a scalar prod-
uct of two phase space functions so that a vector space lan-
guage can, and is, used in the rest of the paper.
While I(t) changes as it evolves with time, only its com-
ponent along the phase space I direction is of importance for
the calculation of s . This is equivalent to determining the
matrix element of the resolvent that is diagonal in I. The
generalization of Zwanzig’s13 projection operator is the pro-
jection operator P onto the 2a11-dimensional subspace
spanned by the components of I
a
P5A u I&& ( ^^ Iu . ~5!
The normalization constant A is introduced to make the pro-
jection operator idempotent
a a a
P 2 5A 2 u I&& ( ^^ Iu I&& ( ^^ Iu 5A u I&& ( ^^ Iu 5P. ~6!
On the assumption that the equilibrium density operator ~dis-
tribution function! is rotationally invariant, and that the flux
operator I has no preference for any particular direction in
space, it follows that ^^ Iu I&& is a 2 a -dimensional tensor
which must be a rotational invariant. ^^ Iu I&& is thus a scalar
multiple of E( a ) , the rotationally invariant tensor of rank 2a
that acts as the Cartesian tensor identity for the 2a11-
dimensional irreducible representation of the three dimen-
sional rotation group.15 Thus
^^ Iu I&& 5aE~ a ! ~7!
with a proportionality constant a determined by taking the
contraction of both sides of Eq. ~7! with E( a ) to show that
a
^^ I( u I&&
a5 ~8!
2 a 11
and by substituting Eq. ~7! into Eq. ~6!,
2 a 11
A5 . ~9!
a
^^ I( u I&&
Since P projects onto the subspace of functions deter-
mined by the components of I, it follows that the transport
coefficient can be written
3454 J. Chem. Phys., Vol. 109, No. 9, 1 September 1998 S. Alavi and R. F. Snider

s 5 lim lim
e →0 N,V→`
iB
~ 2 a 11 ! V
K U
I( P
a 1
i e 2L
PI L , ~10! s 5 lim
e →0 N,V→`
lim
iB
~ 2 a 11 ! V

KK U LL
N/V5const. N/V5const.

a 1
3 I( I
involving the projection of the resolvent operator. This can 1
z2PL LP
be expanded in terms of the resolvent of the projected Liou- z2 ~ 12P! L~ 12P!
ville operator according to ~for convenience and possible
a
generalization, this is expressed in terms of z5i e ) iB
5 lim lim ^^ I( u X&& , ~14!
e →0 N,V→` ~ 2 a 11 ! V
N/V5const.

1 1 where u X&& is defined by

P P5P @ z2L1 ~ 12P! L~ 12P!
z2L z2PLP
1
1 u X&& 5 u I&& . ~15!
1
1PL~ 12P! 1 ~ 12P! LP# P z2PL LP
z2L z2 ~ 12P! L~ 12P!
Inverting this defining relation and using the e →0 limit, it is
seen that
1 1 1
5P P1P PL~ 12P! P,
z2PLP z2PLP z2L 1
u I&& 52PL LPu X&& . ~16!
z2 ~ 12P! L~ 12P!
The phase space inner product of this with I implies that
1 1
5P P1P PL~ 12P!

3
z2PLP
1
z2PLP

LP
1
P. ~11!
E~ a ! 52A ILK 1
z2 ~ 12P! L~ 12P!
a
UL
L I ( A ^^ Iu X&& . ~17!

z2 ~ 12P! L~ 12P! z2L Since both brackets in this expression are 2 a rank rotation-
ally invariant tensors, they are each a scalar multiple of E( a ) .
Manipulations similar to those stated in Eqs. ~7! and ~8! give

K UL
The first term describes the evolution within the I subspace
while the second term describes the influence of the rest of 2A a 1 AV s
the function space on the subspace determined by I. Solving 15 I( L LI , ~18!
2 a 11 z2 ~ 12P! L~ 12P! iB
for the projected resolvent gives
which gives an expression for the transport coefficient in the
form
1 1 1 A 2V
P P5 . 5 lim lim
z2L 1 s e →0 ~ 2 a 11 ! B
z2PLP2PL ~ 12P! LP N,V→`
z2 ~ 12P! L~ 12P! N/V5const.

K UL
~12!
a i
3 I( L LI . ~19!
z2 ~ 12P! L~ 12P!
Since the I’s for the transport coefficients belong to irreduc-
ible representations of the rotation group with time indepen- It can be noted that the above manipulations have led to an
dent normalization a, the projected Liouville operator PLP operator combination that has the structure of an N-particle
50. The proof13 states that ^^ Iu Lu I&& can be written as transition operator. The e →0 limit of a transition operator
has well understood convergence properties.
^^ Iu İ&& , which is proportional to d ^^ Iu I&& /dt. Since the equi- Zwanzig13 simplified this to the equivalent form
librium ensemble is constant with time, so is ^^ Iu I&& , its time
derivative vanishes, PLP50 and Eq. ~12! is simplified to 1 A 2V
5 lim lim
s e →0 N,V→` ~ 2 a 11 ! B
N/V5const.

K UL
1 1
P P5 . ~13! a i
z2L 1 3 I( L LI . ~20!
z2PL LP z2 ~ 12P! L
z2 ~ 12P! L~ 12P!
His derivation involved the generalized Master equation with
the consequent identification of the transport coefficient as
With this expression for the projected resolvent, the the inverse of the Laplace transform of the memory kernel of
transport coefficient expression, Eq. ~10!, becomes that equation.

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J. Chem. Phys., Vol. 109, No. 9, 1 September 1998 S. Alavi and R. F. Snider 3455

III. ONE-PARTICLE PROPERTIES AT LOW DENSITY then the inner product of Eq. ~8! is N(2 a 11) and the nor-
malization factor for the projector of Eq. ~5! becomes A
For a low density gas, the measured physical properties 51/N.
are all associated with individual molecular attributes. In par- Equation ~19! for the transport coefficient can then be
ticular, transport is due solely to the kinetic motion of the written
individual molecules, as distinct from transport associated
with the intermolecular potential, which becomes significant 1 V
5 lim lim
at higher densities. Collisions disrupt these kinetic motions, s e →0 N,V→` BN ~ 2 a 11 !
N/V5const.
giving rise to the transfer of motion from one molecule to
another, interrupting the transport and giving rise to the re-
sistance to flow of the fluid ~viscosity!, finite transfer of en-
ergy ~thermal conductivity!, etc. In such cases: ~1! the phase
3 K a
J1 ( L
i
z2 ~ 12P! L~ 12P!
LI UL
function I is a sum of one particle properties; ~2! the equi- ~ N21 ! V
librium averaging involves a distribution function f (N) which 5 lim lim
e →0 N,V→` BN ~ 2 a 11 !
is a product of one particle Boltzmann factors; ~3! the inter- N/V5const.

K UL
molecular potential for the system is pairwise additive so that
a i
the Liouville operator has kinetic and potential contributions
3 J1 ( V12 LI
z2 ~ 12P! L~ 12P!
L5 (j Kj 1 j,(l Vj l ; ~21!

and ~4! termolecular collisions are to be ignored. It is the

[ lim
e →0 N,V→`
lim
~ N21 ! V
BN ~ 2 a 11 !
E a
dx1 J1 ( B~1N ! , ~26!
N/V5const.
combination of these four restrictions that are used to derive
on the basis, first that I is a sum with all particles contribut-
otherwise exact expressions for the transport coefficients in-
ing equally, and second, that only the potential part of L has
volving only binary collisions.
any effect on J1 , with particle 2 being a typical particle in-
In later sections the general formalism developed here is
teracting with particle 1. In the following a closed expression
specialized, first to identify how all higher Sonine polyno-
for the vector valued function
mial terms of the Chapman–Cowling solution of the Boltz-
mann equation arise from the time correlation formalism.
This shows how the binary collision expressions derived
B~1N ! [ E dx~ N21 ! V12
i
z2LP
LIf ~ N ! , ~27!
here are the same as those obtained by exactly solving the will be calculated. The shorthand notation LP[(12P)L(1
Boltzmann equation. Second, the formalism is adapted to 2P) has been introduced for convenience.
show how the Boltzmann equation expressions for mixtures Since, in Eq. ~27! for B(N)
1 , the pair 12 is interacting, it is
arise from the time correlation function formalism. It does appropriate to identify this interaction with a binary collision
not appear that either of these detailed connections have been between this particular pair of particles. This can be accom-
made previously for the general case. plished by introducing the resolvent for the pair evolution
On the basis that any physical observable is associated operator L12[K1 1K2 1V12 , so that, after reorganization,
with individual molecular attributes, it follows that the flux I B(N) can be written in the form
1
is an additive property of the individual molecules in the
system,
N
B~1N ! 5 E dx~ N21 ! V12
i
z2L12

I[ (
j51
Jj , ~22!
3 @ z2LP1 ~ 12P! L~ 12P! 2L12#
1
LIf ~ N !
z2LP

E
whose contribution, J j , from molecule j is a function only of i
that molecule’s momentum, p j . For convenience of notation 5 dx~ N21 ! V12 LIf ~ N !
it is assumed that J j is normalized so that z2L12

a
^^ J j u J j && 5E~ a ! , equivalently ^^ J j ( u J j && 52 a 11. ~23!
1 E dx~ N21 ! V12
i
z2L12 F(k, l
klÞ12
Vk l 2PL
G
Provided the distribution function for the gas 1
3 LIf ~ N ! . ~28!
N z2LP
wj
f ~ N !5 )
j51 V
, ~24! This is a generalization of Watson’s14 binary collision expan-
sion. Since the two left-most operators in the integrals of this
is a product of one-particle distribution functions which are equation involve only particles 1 and 2, and these in a sym-
normalized metrical manner, the integration over all the other particles
can be carried out before getting to these operators. More-

Ew V
j
dx j 51, ~25!
over, the equations can be simplified by emphasizing only
the behavior of one particle, chosen as that labeled by 1, with
particle 2 taken into account by the introduction of the
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3456 J. Chem. Phys., Vol. 109, No. 9, 1 September 1998 S. Alavi and R. F. Snider

permutation operator P 12 . Further simplification is obtained

by introducing the 2-particle transition operator R1 [
n
w1
E dx2 iT12~ 11 P 12! w 1 w 2 . ~31!
1 1
T12[V121V12 V 5V12 ~ z2K12! ~29!
z2L12 12 z2L12
and the reduced pair distribution function, f 12(2) Technically, terms involving a third particle, such as
5 * dx(N22) f (N) 5 w 1 w 2 /V 2 . In terms of these quantities, the * dx3 V13(J1 1J3 ) w 1 w 2 w 3 arise in simplifying the integral of
first term in B(N)
1 is Eq. ~30!. It is argued that the potential between particles 1

E
and 3 depends only on the relative position r13 and the inte-
i
dx~ N21 ! V12 LIf ~ N ! gral over the position of particle 3 can be converted to that
z2L12
relative position whose integration then gives 0. Similarly,

5 E dx2 V12
i
V ~ 11 P 12! J1 f 12~ 2 !
z2L12 12
the definition of T12 involves a separate V12 factor that
doesn’t appear in the first line of Eq. ~30! but whose integra-
tion over the position of particle 2 gives a null value. This
5 E dx2 iT12~ 11 P 12! J1 w 1 w 2 /V 2 5
w1
R J ,
VN 1 1
~30! same procedure is not valid for the term that has been kept
because of the presence of other r12 dependent terms.
where the binary ~linearized Boltzmann! collision operator, The remaining terms in B(N) 1 are handled in a similar
R1 is defined as manner, to give

E dx~ N21 ! V12

i
z2L12 F(
k, l
Vk l 2PL G 1
z2LP
LIf ~ N !

5 E dx2 T12
i
z2K12
~ 11 P 12! ~ N22 ! F E dx~ N22 ! V132J1
f ~122 !
N
E dxN IL G 1
z2LP
LIf ~ N !

5 E dx2 T12
i
z2K12
~ 11 P 12! ~ N22 ! F E dx~ N22 ! 2J1 f ~122 ! ~ N21 ! E G
dxN J1 V13
1
z2LP
LIf ~ N !

5 E 1
F
dx2 iT12 ~ 11 P 12! ~ N22 ! B~12N ! 2 f ~122 ! J1 ~ N21 !
z
E G
dx1 J1 B~1N ! ~ 2i ! ~32!

with a reasonably obvious definition for B(N)

12 , which will be w 2 ~ N21 ! w 2 ~ N !
discussed further below. The last term of Eq. ~32! can be 5 B ' B1 . ~35!
V 1 V
simplified by the use of the projection operator

P0 [ w 1 J1 (
a
E dp1 J1 . ~33! The first approximation is based on the idea that this term
inherently involves the interaction ~collision! between par-
This is a projection onto the subspace determined by J1 in ticles 1 and 3 with particle 2 entering only indirectly as a
the momentum space of particle 1. On collecting the various spectator for this collision. On the basis that only binary
expressions, B(N)
1 satisfies the equation collisions are to be retained, it is thus appropriate to ignore

E
w1 i any interaction with particle 2, thus its distribution function
B~1N ! 5 R1 J1 2 dx2 iT12~ 11 P 12! can be passed through the remaining combination of resol-
VN z
vent and Liouville operators. The remaining integral cor-

F
3 ~ N22 ! B~12N ! 2
N21
V2
w 2 P0 E G
dr1 B~1N ! . ~34!
rectly involves only N21 particles, which is the second
equality. It is a consequence of these approximations that
termolecular collisions are eliminated. Finally, if N is very
The function B(N) large, the B(N21) function is essentially the same as B(N)
1 , the
12 can be simplified with the following ap- 1
proximations second approximation. Consistent with this independence of
N, the system size labelling on B1 is dropped in the remain-
B~12N ! 5 E dx~ N22 ! V13
i
z2LP
LIf ~ N !
der of this paper. Another simplification of the same type is
(N21)/V'(N22)/V'n. Since the system is homoge-
neous, B1 is position independent, it follows that * dr1 B1
'
w2
V
E dx~ N22 ! V13
i
z2LP
LIf ~ N21 ! 5VB1 and Eq. ~34! becomes a closed equation for B1 , spe-
cifically

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J. Chem. Phys., Vol. 109, No. 9, 1 September 1998 S. Alavi and R. F. Snider 3457

w1 iw1 1 which can be solved for (12P0 )B,

B1 5 R J 2 R ~ 12P0 ! B1 . ~36!
VN 1 1 z 1 w1
The object is now to solve this equation. As a closed equa- z w
tion for a one-particle function, there is no need to retain the ~ 12P0 ! B5 ~ 12P0 ! RJ.
1 VN
particle label, so this is dropped in the further development. z1i ~ 12P0 ! w R ~ 12P0 !
Since Eq. ~36! contains both the full B and its projected w
part (12P0 )B, it is appropriate to first solve for the (1 ~38!
2P0 ) part of B. Left multiplying Eq. ~36! by (12P0 ) gives
w i 1 Substituting this back into Eq. ~36!, taking the tensor con-
~ 12P0 ! B5 ~ 12P0 ! RJ2 ~ 12P0 ! w R ~ 12P0 ! B,
VN z w traction with J, and integrating over the momentum of par-
~37! ticle 1 gives

E a
dpJ( B5
1
VN F E a
dpJ( w RJ2
i
z
E a
dpJ( w R
w
1 z
1
z1i ~ 12P0 ! w R ~ 12P0 !
w
~ 12P0 ! w RJ
G
5
1
VN F
~ 2 a 11 ! R0,02 E a 1
dpJ( w R ~ 12P0 !
w
1
1
~ 12P0 ! w R ~ 12P0 !
w
~ 12P0 ! w RJ .
G ~39!

E
The operator inverse can be evaluated if an appropriate com- 1 V2 a
plete orthonormal basis $ O j % of 1-particle functions is intro- 5 lim lim dpJ( B
duced. This basis must be restricted to functions orthogonal s e →0 N,V→` ~ 2 a 11 ! B
N/V5const.

F SD G
to the collisional invariants, equivalently orthogonal to the
eigenvectors of R whose eigenvalues are zero. Furthermore, ^v& 1
for convenience, the basis should have J5O0 (p) as a par-
5
B
S0,02 ( S0,j
j, l Þ0 S
Sl ,0 . ~43!
j, l
ticular member of the basis and all members should belong
to the same (2 a 11-dimensional! irreducible representation The result usually presented ~see for example Ref. 10! as the
of the 3-dimensional rotation group, with orthonormalization evaluation of a dilute gas transport coefficient according to
determined by the time correlation function method is the first term in Eq.
~43!, i.e., the S0,0 term. Here it is seen how correction terms

E dpO j ~ p! w Ol ~ p! 5 d j l E~ a ! . ~40!
to this standard approximation arise within the binary colli-
sion approximation of the time correlation function.

Matrix elements of R, after taking their rotational invariance

into account, are usually expressed in term of kinetic cross
sections S,16–18 namely
E dpO j w ROl [R j, l E ~a!
5n ^ v & S j, l E
wherein ^ v & is the average relative speed of the pair of col-
liding particles. The projector 12P0 then merely selects out
the O j ÞO0 elements of the basis, with the consequence that
IV. THE COMPLETE SONINE EXPANSION
In solving the Boltzmann equation for the purpose of
~a!
, ~41! calculating the transport coefficients, the distribution func-
tion is expanded about local equilibrium and after eliminat-
ing the time derivatives, a linear equation is obtained for the
perturbation of the distribution function from local equilib-
rium, f. The inhomogeneous term in this equation is, for
each of the viscosity, thermal conductivity and ~for mixtures!

E F SD G
a diffusion coefficient, the respective flux of momentum, en-
2 a 11 1
dpJ( B5
VN
R0,02
j, l
(Þ0 R0,j R
Rl ,0
ergy and species mass. For a given transport property, the
linear ~Chapman Enskog! equation18–20 can be expressed in
j, l

F SD G
the present notation as
~ 2 a 11 ! ^ v & 1
5
V 2
S0,02 ( S0,j
j, l Þ0 S
Sl ,0 . J5Rf ~44!
j, l

~42! and the transport coefficient is given by

Finally, the transport coefficient is determined by taking

the appropriate limit of this expression, namely
s5
nB
2 a 11
E a
dpJ( fw , ~45!

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3458 J. Chem. Phys., Vol. 109, No. 9, 1 September 1998
with the factor nB chosen to agree with the normalization of
Eq. ~2!. There are solvability and uniqueness conditions that
must be satisfied, the only one of importance for the present
discussion being the uniqueness conditions, namely that the
perturbation f must be orthogonal,
E dpfcw 50,
to any ~collisional! summational invariant c, these being the
mass, momentum and energy.
The solution of the Chapman Enskog Eq. ~44! can be
calculated in a number of different ways. A first approxima-
tion is to assume f5bJ is proportional to J. In that case, a
matrix element of Eq. ~44! with J gives
b51/n ^ v & S0,0
and the transport coefficient
s 5B/ ^ v & S0,0 ,
compare with the first term in Eq. ~43!. An exact solution can
be obtained by making a complete expansion of f and tak-
ing appropriate matrix elements with all the basis elements.
A more formal method is to introduce the inverse operator
R 21 ~subject to the orthogonality condition! and formally
write the transport coefficient as
E SD
a questions. But except when treating transport properties in
nB 1
s5 dpJ( w J.
2 a 11 R off diagonal in the eigenstates of the internal state Hamil-
Introduction of a complete orthonormal basis set allows the
inverse operator to be calculated. The classic orthogonal ba-
sis used in solving the Boltzmann equation are functions
consisting of a product of the appropriate tensor in reduced
momentum W[p/ A2mk B T and a Sonine ~equivalently as-
sociated Laguerre! polynomial in W 2 . The normalized ver-
sion of this is16
La s ~ W! [ A Ap ~ 2 a 11 ! G ~ s11 !
2 a 11 ~ a ! ! 2 G ~ s1 a 13/2!
L sa 11/2~ W 2 !@ W# ~ a ! ,
(a)
where @ W# is the symmetric traceless tensor of rank a
~and belonging to an irreducible representation of the 3-
dimensional rotation group!. For the shear viscosity and dif-
fusion, the flux function J5La 0 corresponds to s50
whereas for the thermal conductivity, J5L11.
The standard method20 of solving Eq. ~44! calculates the
matrix inverse and expresses the above matrix element as the
ratio of two determinants. In contrast, if the matrix represen-
tation of R is divided into parts associated with and without
J, this can be most efficiently accomplished with the use of
the projector P0 introduced in the last section. Since it is the
projected element of the inverse operator that appears in the
transport coefficient, the analog of Eq. ~12! is
1 1
P0 P 5
R 0 1
P0 RP0 2P0 R
~ 12P0 ! R~ 12P0 !
RP0
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S. Alavi and R. F. Snider
As the $0,0% matrix element of this inverse operator, the
transport coefficient is then given by
F SD G
1 1 1
5 R 2
s nB 0,0 j, l (Þ0 R0,j R
Rl ,0 ~52!
j, l
~46!
which, when converted to kinetic cross sections, is identical
to Eq. ~43!.
The above formalism has inherently assumed that the
molecules have only translational states. In case the mol-
ecules have internal states, the flux operators will in general
involve the internal states and the complete set of functions
must span the internal states as well as the translational
states. It is then necessary to include a trace over the ~quan-
tum! internal states as well as the integration over the posi-
tion and momentum. To correctly formulate this mix of clas-
~47! sical and quantum descriptions the distribution function must
be replaced by a quantity which is simultaneously a Wigner
function21 for the translational states and a density operator
~48! in the internal states. A further complexity is that a complete
set of internal state operators includes operators that do not
commute with the internal state Hamiltonian. When acting
on such an operator O, the z parameter in the definition, Eq.
~29!, of the collision superoperator T requires z5 v 1i e to
have its real part equal to the eigenvalue v of K when acting
on O ~that is, v is the difference of energies of the ket and
bra Dirac states of O!. This work does not address such
~49! the presence of a field, it has been argued that terms that are
tonian are rapidly phase randomized.22 As such, the set of
operators used for expansion can be limited to those that
commute with the internal state Hamiltonian. With this con-
straint, the formal development is the same as above, except
that the basis elements only spans the diagonal-in-internal-
state-energy part of the space of operators on internal states.
V. TRANSPORT COEFFICIENTS OF A BINARY
MIXTURE
The collisions between molecules of the same species
~50! behave very differently from collisions between different
species, thus it is not sufficient to use an average of the
transport coefficients of the individual species in a mixture,
but rather it is necessary to take into account how they in-
fluence each other. It is thus necessary, even at the lowest
order of approximation, to include a separate flux function
for each of the species. This section discusses the simplest
case of a nonreacting ideal gas binary mixture, each species
having a single basis function ~that is, ignoring the role of
higher Sonine polynomials or other dependences on rota-
tional, electronic, etc. internal states!. The method of formu-
lation is to directly adapt the general treatment of Sec. III by
considering the two species, labeled a and b, as being
equivalent to two different internal states of a molecule, with
of course the mass now dependent on the internal state.
The sum over molecular states now must include a sum-
P0 . mation over the species, using here a generic label s,
~51!
E dx5 (s EE dp dr, ~53!
J. Chem. Phys., Vol. 109, No. 9, 1 September 1998 S. Alavi and R. F. Snider 3459

as well as the translational degrees of freedom of the corre-

sponding species ~ignoring the possible presence of other
internal states!. Corresponding to this, the one particle distri-
12P0 ⇔ S X b Pa
2 ~ P0 ! ba
2 ~ P0 ! ab
X b Pb
D 5 z ( j† .
a
~62!

bution function ~density operator! for a typical molecule has The factorization is recognized as a consequence of the es-
the structure sential factorization of (P0 ) ss 8 , with the two-dimensional
vectors defined as
w w
5 (s x s X s Vs , ~54!

S D E S D
V
w a Ja X b Ja
involving the identification state x s of species s, the normal- z⇔ j⇔ dp . ~63!
2 w b Jb 2X a Jb
ized species distribution function w s /V and its mole fraction
X s . For an ideal gas mixture, the higher ordered distribution
functions can be considered as products of the one-particle Equation ~62! represents, of course, the projection onto the
distribution functions, compare Eq. ~24!, ignoring the con- vector z in the space of species flux.
straint that only X a N of the N molecules can be of species a. A transport coefficient of a one-particle property is given
To make the properties of the mixture clearer, it is useful to by Eq. ~26! with the integral evaluated by Eq. ~39!. The latter
introduce a two-dimensional species vector space, so that the depends on the evaluation of an inverse of a projected colli-
species projection operators become sion operator. Since in the present case this projection is one

SD SD S D
dimensional, it follows that
1 0 X aw a
x a⇔ x b⇔ w⇔ . ~55!
X bw b
F G
0 1
21 a
1 1
Finally, the flux operator also has contributions from both ~ 12P0 ! w R ~ 12P0 ! 5 z ( j† ~64!
w Den
species, thus

J5 (s ` s Js , ~56! in which the denominator is

where ` s are the projectors onto their respective species, 1 a 1

namely Den5 j† ( w R z
2 a 11 w

` a⇔ S D 1
0
0
0
` b⇔ S D
0
0
0
1
. ~57! 5X b Ra,a 1X a Rb,b 2X a Ra,b 2X b Rb,a . ~65!

The analogous trace over molecular states becomes the row This involves the collision matrix elements
vector
1
V
TrJ5 (s E dpJs x †s ⇔ E dp~ Ja Jb ! . ~58! Ra,a 5
1
2 a 11
E a
dpJa ( w a RJa

Equations ~26! and ~39! can be directly adapted to the calcu-

lation of a mixture transport coefficient, but now the projec- 5nX a ^ v & a S S UD
a0 a
a0 a aa
1nX b ^ v & ab S S UDa0 a
a0 a ab
~66!
tor P0 onto the flux function J becomes the two-dimensional
matrix with components

S E D
and

~ P0 ! ss 8 5 w J(
a
dpJ
ss 8
5 x s X s w s Js (
a
E †
dpJs 8 x s 8 ,
Ra,b 5
1
E a
dpJa ( w a RJb 5nX b ^ v & ab S S UD
a0 a
,
~59! 2 a 11 a0 b ab
~67!
or in matrix form
together with the analogs obtained by interchanging species

P0 ⇔ S X a w a Ja
X b w b Jb
DE a
( dp~ Ja Jb ! . ~60!
a and b. Note that when the flux operators are associated
with the same species, there are two types of terms, one in
which the binary collision is between molecules of the same
There are analogous species flux projectors species and another when the collision partner is a molecule
of the other species. The ‘‘telephone’’ notation of the cross

Ps ⇔ w s Js (
a
E dpJs S d a,s
0
0
d b,s
D . ~61!
sections involves a classification of the irreducible represen-
tation for the translational ~here a ) and internal state ~here 0!
motions, the species carrying the flux function and which
Within the constraint of having only two species and only pair of molecules are colliding, see Refs. 17 and 18.
the flux operators Js for these species, the identity is equiva- Equation ~39! requires the evaluation of the inner prod-
lent to Pa 1Pb , so that the projector 12P0 is uct

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3460 J. Chem. Phys., Vol. 109, No. 9, 1 September 1998 S. Alavi and R. F. Snider

E a 1 a The formalism given is completely general and can be

dpJ( w R z( j† w RJ used in the low density limit for any of the applications
w stated in the Introduction. It only involves the assumption

5 E a
dp~ Ja Jb ! ( w R S Ja /X a
2Jb /X b
D a
(
that I is a sum of one particle properties and the restriction to
binary collisions. The implementation of the latter is the set
of approximations made in Eq. ~35!. The meaning of the

3 E dp~ X b Ja 2X a Jb ! w R SD Ja
Jb
binary collision operator R will be different for each case,
but the formalism is otherwise the same.
For an I which includes two-particle phase space func-

5 ~ 2 a 11 ! Ra,a 2 F Xa Xb
R 1 R 2Rb,b
X b a,b X a b,a G tions, or for cases where the spatial correlations of particles
can no longer be neglected, the manipulations presented in
this paper must be changed, and it is not clear whether a
3X a X b @ Ra,a 1Ra,b 2Rb,a 2Rb,b # closed expression for B can be obtained. The nature of some
of the expansions are, however, the same in these cases, and
5 ~ 2 a 11 ! X a X b @ Ra,a 1Ra,b 2Rb,a 2Rb,b # 2 . ~68! by adaptation of the formalism, a density expansion for the
The last equality depends on the symmetry of the Boltzmann transport coefficients can be obtained. This method of ap-
collision integral proach is again general and will be illustrated for viscosity
and thermal conductivity in future work.
X a Ra,b 5X b Rb,a . ~69!
Also required is the matrix element
ACKNOWLEDGMENTS

R0,05
1
2 a 11
E a
dpJ( w RJ
5X a Ra,a 1X a Ra,b 1X b Rb,a 1X b Rb,b .
Putting these results into Eqs. ~26! and ~39!, together with
simplifying the result by an extensive use of the symmetry of
Eq. ~69!, the mixture transport coefficient becomes
s X b Ra,a 1X a Rb,b 2X a Ra,b 2X b Rb,a
5 .
nB Ra,a Rb,b 2Ra,b Rb,a
This expression is exactly the same as that obtained from the
Boltzmann equation, as found for example in McCourt,
et al.18 for binary mixtures where it is expressed in terms of
kinetic cross sections.
VI. DISCUSSION
The original motivation for this work was to obtain ex-
pressions for the density corrections of the transport coeffi-
cients. As an analogous problem, it was asked how correc-
tions to the lowest order approximation to the Boltzmann
equation could be derived from the time correlation formal-
ism. Naturally the density corrections require keeping the
fluxes associated with collisional transfer, but in the low den-
sity limit, the effect of such terms in I, and the effects of
spatial correlation of the particles may be neglected. Even
the restricted cases considered here illustrate the elaborate
coupling of terms that may arise when evaluating Eq. ~2! to
find corrections to the lowest order expressions for the gas
transport coefficients. But the method introduced here de-
duces from the time correlation function formulation, expres-
sions for the transport coefficients that immediately include
the higher ordered Sonine polynomials and the analogous
expressions for mixtures. Both derivations appear to be
novel.
This work was supported in part by the Natural Sciences
and Engineering Research Council of Canada. S. A. thanks
~70! the University of British Columbia for a University Graduate
Fellowship.
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