Physica A, 1999
On the statistical
hydrodynamics for a binary mixture of magnetic and nonmagnetic
particles
Mryglod I.M., Rudavskii Yu.K., Tokarchuk M.V.,
Batsevych O.F.
Abstract:
Dynamic properties of a binary mixture of magnetic and nonmagnetic particles are considered with the help of the method of nonequilibrium statistical operator. The generalized hydrodynamic equations are derived and analyzed. On this basis hydrodynamic collective modes spectrum was calculated. The expressions for sound velocity and damping coefficients of collective hydrodynamic modes are found. We propose the consistent scheme for calculation of time correlation functions in the hydrodynamic limit and discuss the expressions found for them in paramagnetic case.
Magnetic liquids, mixtures of magnetic and nonmagnetic particles in the external fields of mechanical or electromagnetic origin, have already taken their significant place in chemical, electronic and other modern technologies. That is why the investigations of the thermodynamical, structural and dynamical properties of liquid magnets are very actual for more deep understanding and forecasting of their behaviour [1,2,3].
The investigation of time-dependent correlation functions as well as generalized transport coefficients of a liquid mixture of magnetic and nonmagnetic particles give us possibility of deep insight into the processes in the systems with coupled classical and quantum peculiarities. One of the most interesting problems is investigation of the behaviour of hydrodynamic collective modes, which describe the properties of heat, sound, and mass fluctuations. From the experimental point of view the investigation of these phenomena as well as effects of ``speed'' sound, spin waves and their dependance on temperature, concentration are very valuable. The explicit information about the volume features of mixtures of magnetic and nonmagnetic particles, molecules is essential in studying of their interaction with active surfaces (metals, semiconductors), where the processes of metallic arrangement, adsorption, desorption, chemical transformation can take place. Another important aspect of this problem is the derivation of expressions for dynamic structure factors. It is known, that these functions can be extract from neutron scattering experiments. Such theoretical study should be based on the statistical approach, on the equations of generalized hydrodynamics, particularly. Similar approach was applied to one-component magnetic mixture [4,5,6,7,8]. The collective modes of Heisenberg ferrofluid were also considered in [8].
Statistical hydrodynamics for a mixture of magnetic and nonmagnetic particles
in an external nonhomogeneous magnetic field
was studied in [9]. There was
formulated the problem of derivation of generalized hydrodynamic equations for
magnetic and nonmagnetic subsystems in the external nonhomogeneous magnetic
field with the help of nonequilibrium statistical operator method for
description both strong and weak nonequilibrium states. Magnetic and nonmagnetic
subsystems were characterized by individual nonequilibrium thermodynamics
parameters. As a result nonequilibrium thermodynamical relations and generalized
equations of hydrodynamics were derived.
This paper is dedicated to the study of a binary magnetic mixture consisting
of magnetic and nonmagnetic particles within the method of nonequilibrium
statistical operator. From the physical point of view this case is more
interesting then that [4,5,6,7,8] of the
one-component mixtures, because for the great ratios of masses of different
component particles it can be treated as a ferrocoloid mixture. On the base
of a set consisting of five parameters of abbreviated description, for the weak
nonequilibrium case the equations of generalized hydrodynamics are derived. For
the microscopic quantities which make up a set of abbreviated description the
expressions of currents were obtained and their contribution to the
thermodynamical quantities and kinetic coefficients, determining dynamics of the
system calculated. The calculation of hydrodynamic collective modes are carried
out with the help of the perturbation theory, yielding two sound-propagation
modes and three purely diffusive modes. The expression for sound velocity
derived generalize that of a singlecomponent ferrofluid [8]. In the chapter 2 we
give briefly the main relations of the method of nonequilibrium statistical
operator [10],
which will be used for finding the equations of generalized hydrodynamics for
the mixture of magnetic and nonmagnetic particles. The definition of the
Hamiltonian of the system will be given in the next chapter. The chapter 4 is
dedicated to finding of the static correlation functions in the limit
. This gives us possibility to find the matrices
of frequencies and memory functions in the Markovian approximation. In the sixth
chapter the collective excitation spectrum in the hydrodynamic limit is derived
and analyzed. In the chapter 7 the problem of calculation of time-correlation
functions is considered. We propose here the scheme which allows to calculate
the weight coefficients describing a partial contribution of each mode to the
hydrodynamic time correlation functions. In some limiting cases (pure
non-magnetic fluid, simple magnetic liquid, etc.) the obtained results are
discussed in comparison with the results known in the literature.
Let us start with the Liouville equation:
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(2.1) |
where classical part of
is determined as a Poisson brackets of the function
with a classical part of the Hamiltonian of the system
and the quantum one - as a commutator with its quantum part,
is a function of phase variables
, where N is a total number of
particles.
Following Zubarev's method of nonequilibrium statistical operator [10] we can rewrite equation (2.1) in the form:
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(2.2) |
where
after the thermodynamical limit,
is so-called quasi-equilibrium statistical operator. Nonzero
right-hand side of the equation (2.2) imposes the boundary conditions, which
destroy the time reversal symmetry of the Liouville equation and choose the
retarded solutions which correspond to the ideas of abbreviated description of
the nonequilibrium state of the system. To restrict our consideration to the set
of slow physical quantities
which are thought to determine nonequilibrium state (the set of
conserved quantities). The Gibbs-like statistical operator
can be found from the extremum problem of information
entropy with fixed parameters of abbreviated description
and normalizing condition
:
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(2.3) |
where the parameters
are defined from the self-consistency conditions:
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(2.4) |
The index
denotes a combination of discrete index i which numerates the variables and wave vector <I>k so, that summation in (2.3)
means:
. Taking into account projecting, the formal solution of equation (2.2)
can be written [10]:
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(2.5) |
where
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(2.6) |
are the generalized fluxes,
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(2.7) |
is the operator of time evolution with the Kawasaki-Ganton projection
operator
, which is connected with the generalized Mori projection operator
by the relation:
effects on the dynamical variables as follows:
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(2.8) |
which have the following properties:
,
,
.
Statistical operator (2.5) determines generalized transport equations in the form [10]:
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(2.9) |
where
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(2.10) |
are the generalized memory functions, or generalized transport kernels. Equations (2.9), (2.10) and (2.4) make up a closed system of nonlinear equations which describe both strong and weak nonequilibrium.
Now we will consider weak nonequilibrium, which allows us to linearize system (2.4), (2.9), (2.10). For the small deviations
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(2.11) |
of averages
from the equilibrium values
, where
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(2.12) |
is the equilibrium statistical operator, deviations of the intensive
quantities
can be easily found from the self-consistency conditions (2.4). In
matrix form:
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(2.13) |
where
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(2.14) | |
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and
means correlation function:
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(2.15) |
which transforms into simple average
in classical case. Now we can rewrite (2.5) in the form
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(2.16) |
where the projection operator is given by
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(2.17) |
For the Laplace transforms of time-dependent functions, using the equality
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(2.18) |
we get the generalized transport equations in the form
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(2.19) |
where
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(2.20) |
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(2.21) |
are the matrices of frequencies and memory functions. The matrix equation for
the Laplace-transforms
of time correlation functions
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(2.22) |
has the structure, similar to that of (2.19):
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(2.23) |
Retarded correlation Green functions can be expressed in terms of time
correlation functions
(which are connected with
by Laplace transformation):
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(2.24) |
Hence, the poles of the retarded Green functions, which give the spectrum of collective modes are determined by matrix equation
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(2.25) |
Let us consider the system consisting of N1 nonmagnetic and N2 magnetic particles posed in external magnetic field. Hamiltonian of such a system can be written as in [12,13], taking into account the interaction with nonmagnetic subsystem:
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(3.1) |
Here and further subscripts
or superscripts in parentheses
indicate nonmagnetic and magnetic subsystem, respectively. Thus H1 and
are the Hamiltonians of nonmagnetic and magnetic subsystems
separately, Hint describes
their interaction and
is the energy of spin interaction with external magnetic field. The
Hamiltonian H1 of nonmagnetic
subsystem can be taken in classical form
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(3.2) |
where
is the momentum of nonmagnetic particle, V(11)
(<I>rjl) is the potential of interaction
between two nonmagnetic particles j and l, which can be chosen for calculations in any
convenient form; and m1 is a mass of
nonmagnetic particle. The term
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(3.3) |
consists of classical, ``liquid'' part H2L which has the same form as H1 and quantum part, which describes spin subsystem and can be taken in Heisenberg-like form. Other terms in (3.1) could be written in the form
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(3.4) |
where V(12)
(<I>rij) is the potential of interaction
between i-th nonmagnetic and j-th magnetic particle,
- external magnetic field. Liouville operator which corresponds to
Hamiltonian (3.1) can be written as follows:
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(3.5) |
where
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(3.6) | |
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(3.7) | |
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(3.8) | |
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(3.9) |
and
is a purely quantum part of Liouville operator, it is determined as a
commutator
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(3.10) |
To study the dynamics near the equilibrium, we have to consider all the
conserved quantities and most slow ones associated with them. For our model five
parameters of abbreviated description
, i=1..5 can be chosen, namely: partial
densities of particle number
,
, densities of momentum
, magnetization
and total energy
. After the Fourier transformation (
), these values can be written as follows:
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(3.11) | |
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(3.12) | |
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(3.13) | |
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(3.14) |
index
indicates spatial
-component of vector, and
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(3.15) | |
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(3.16) |
For our set of variables
, the quantum equations of motion have the following form (see
Appendix)
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(3.17) | |
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(3.18) |
for the scalar
and vector
variables respectively. Terms Ri (<I>k),
appeared due to nonhomogeneous external magnetic field. When we assume
that
is homogeneous, these terms disappear and variables
become conserved.
When we assume the external magnetic field is static, homogeneous and
directed along the '0z' axis,
, the '0z' component of magnetization density
becomes conserved, see A.10. That is why for such conditions
can be chosen as a parameter of abbreviated description for the
hydrodynamic region. So, for analysis of the generalized hydrodynamic equations
(2.19) one needs to calculate the static correlation functions constructed on
the variables
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(4.1) |
Let us define static correlation function
as an average of deviations:
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(4.2) |
contrary to (2.15), where it was defined as a simple average. In order to
give some thermodynamical interpretation of correlation functions we chose the
equilibrium statistical operator (2.12) as a Gibbs distribution for the grand
canonic ensemble
,
:
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(4.3) | |
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(4.4) | |
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(4.5) |
where
is the thermodynamical potential,
is the inverse temperature,
are the quantities (4.1), taken with <I>k=0:
; and b is an '0z' component of the
external magnetic field.
For an arbitrary operator
and parameter
it is easy to prove the equation
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(4.6) |
where the average
is performed with the distribution (4.3). So, for example, if
,
, we get:
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(4.7) |
Here and further the quantity, written by a capital letter denotes the
average value of corresponding operator written by a small letter, for instance,
. In the same manner with the help of (4.6) we can connect other
correlation functions with thermodynamical quantities:
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(4.8) | |
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(4.9) | |
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(4.10) | |
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(4.11) |
As we see in (4.8)-(4.11), the set of
is not orthogonal, in sense that nondiagonal elements of matrix
do not vanish. But often it is more convenient to work with
orthogonalized set of dynamic variables. Here we use the procedure of
orthogonalization, which orthogonalize all variables one by one except of first
two -
and
, so only the block (2 x 2) of matrix
which includes correlation functions
will be nondiagonal. At first we introduce the projection operator:
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(4.12) |
where
means {ij}-element of matrix (2 x 2), which is inverse to the block
of the matrix of static correlation functions
. And consider `projected' magnetization defined by
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(4.13) |
It is obvious that
is orthogonal to
and
in the sense, that
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(4.14) |
Introducing the projection operator
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(4.15) |
we can construct so-called `enthalpy' operator
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(4.16) |
which is orthogonal to all previous operators, i.e.
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(4.17) |
The momentum operator
is orthogonal to all variables intrinsically.
We must note, that projection with the help of operators (4.12), (4.15) means
transition to another ensemble, for example, projection like in (4.13) means
transition from
to (N,V,T,b)
ensemble. Really, magnetic susceptibility in (N,V,T)-ensemble is defined on
`projected' variable
:
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(4.18) | |
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Using (4.6) we can prove one more equality for entropy and arbitrary
parameter
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(4.19) |
and for specific heat in
-ensemble we will have: ![]()
Fulfilling transition to (N,M,V,T)-ensemble like in (4.18), we obtain
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(4.20) |
For the operator
we have the equalities
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(4.21) | |
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(4.22) |
where
is a mass of our mixture, c1 and c2 are the concentrations of nonmagnetic and
magnetic particles, correspondingly.
Taking into account the relations (4.13), (4.14), (4.16), (4.17), (4.20) -
(4.22), one sees, that the set of variables
is orthogonalized in the sense discussed above. Generalizing obtained
results, we can introduce new set of dynamic variables ( <I>k-dependent)
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(4.23) |
which are mutually orthogonal. One exception is for variables
and
which are not mutually orthogonal. For
and
one has
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= |
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(4.24) |
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= |
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= |
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(4.25) |
where
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(4.26) | |
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(4.27) |
The correlation functions of these quantities can be considered as generalization of well-known thermodynamical derivatives (4.7) - (4.11), (4.18), (4.20), (4.21), for nonzero values of <I>k. Hence,
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(4.28) | |
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(4.29) | |
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(4.30) | |
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(4.31) |
where Sij(<I>k),
defined in (4.28) are so-called partial structure factors,
and CN,M(<I>k) are
the generalized susceptibility and specific heat for the mixture of magnetic and
nonmagnetic particles, respectively.
Taking into account the symmetry of the correlation functions under time inversion and spatial symmetry operations, or performing direct calculations, one can prove, that:
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(5.1) |
Because of the symmetry conditions
for calculation of frequency matrix we must find only correlation functions, which involve momentum:
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(5.2) |
For
one can prove that (see [8])
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(5.3) |
where U(<I>rN) is the total potential energy:
Let us find now pressure of the system, which follows from the equilibrium treatment
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(5.4) |
where
is the thermodynamical potential (4.5). Imposing
to be V-dependent by
substitution
in potentials V(11), V(12), V(22), J, we
can get, after some simplifications
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(5.5) |
Comparing (5.3) and (5.5), we obtain
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(5.6) |
Results (5.6) show that in system with `isotropic' potential energy (which is
a function of |<I>r|, and does not depend on its
direction) in homogeneous external field
, the pressure, defined from equilibrium treatment can be expressed
through the average of the stress tensor. With the help of (4.6) now we get
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= |
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= |
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(5.7) |
Let us introduce now scalar longitudinal momentum
, as a component of vector momentum
, oriented along the vector <I>k . From the equation (5.7) we
conclude, that in isotropic system only longitudinal components make
contribution to the matrix of memory functions, correlation functions of
transverse components are equal to zero. In the same way as (5.7) was obtained
we can obtain other correlation functions with the longitudinal current
in the limit
, (k=|<I>k|)
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(5.8) | |
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(5.9) |
or for our set of orthogonalized variables
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(5.10) |
Using Gibbs-Duhem equation
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(5.11) |
one can write the right-hand sides of equation (5.10) as follows
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(5.12) |
where
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(5.13) | |
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(5.14) |
are the coefficients of magnetostriction, isothermal compressibility and
isobaric thermal expansion for the mixture of magnetic and nonmagnetic
particles, respectively. The value
in equation (5.12) is defined at constant magnetization M. After some algebra with the help of Gibbs-Duhem and
Maxwell relations, we get
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and
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(5.15) |
Now making generalization for
we can write some elements of matrix
as follows
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(5.16) | |
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(5.17) | |
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(5.18) |
Elements, involving densities of particle number, as follows from (5.8) and (2.20), read:
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= |
|