Abstract
We review a non-relativistic current algebra symmetry approach to constructing the Bogolubov generating functional of many-particle distribution functions and apply it to description of invariantly reduced Hamiltonian systems of the Boltzmann type kinetic equations, related to naturally imposed constraints on many-particle correlation functions. As an interesting example of deriving Vlasov type kinetic equations, we considered a quantum-mechanical model of spinless particles with delta-type interaction, having applications for describing so called Benney-type hydrodynamical praticle flows. We also review new results on a special class of dynamical systems of Boltzmann–Bogolubov and Boltzmann–Vlasov type on infinite dimensional functional manifolds modeling kinetic processes in many-particle media. Based on algebraic properties of the canonical quantum symmetry current algebra and its functional representations, we succeeded in dual analysis of the infinite Bogolubov hierarchy of many-particle distribution functions and their Hamiltonian structure. Moreover, we proposed a new approach to invariant reduction of the Bogolubov hierarchy on a suitably chosen correlation function constraint and deduction of the related modified Boltzmann–Bogolubov kinetic equations on a finite set of multi-particle distribution functions. There are also presented results of application of devised methods to describing kinetic properties of a many-particle system with an adsorbent surface, in particular, the corresponding kinetic equation for the occupation density distribution function is derived.
Keywords:
kinetic equations; Bogolubov chain; multi-particle distribution function; current algebra; Wigner representation; functional equations; reduction theory; Lie–Poisson brackets; invariant functional submanifolds; surface adsorption centers PACS:
11.10.Ef; 11.15.Kc; 11.10.-z; 11.15.-q; 11.10.Wx; 05.30.-d
1. Introduction
As it is well known [1,2,3,4,5,6,7,8], the objective of the kinetic theory of many-particle dynamical systems is to explain the properties of macroscopic non-equilibrium state of gases (or liquids) in terms of microscopic properties of individual gas molecules and interaction forces between them. The main task of this theory is to provide microscopic explanation of the fact that a great variety of many-particle flows may be described with Navier–Stokes hydrodynamical equations, as well as to find analytical expressions for viscosity and thermal conductivity coefficients in terms of microscopic properties of molecules and other characteristics. Kinetic theory of gases takes origin in classic works of Daniel Bernoulli, Rudolf Clausius, and especially of James Clerk Maxwell, who was the first to apply statistical methods to gas properties calculations, having realized that random gas molecules movement may be described by means of distribution functions. Apart from the distribution form, Maxwell has also found the transport equation for mass. He has found “microscopic” expressions for transport coefficients for gas constituted by the so-called Maxwell molecules, which interact through push forces, which are inversely proportional to the interparticle distance in the fifth power. He has also shown that the viscosity and thermal conductivity coefficients do not depend on the gas density. Another significant contribution to the statistical mechanics theory was made by Boltzmann, who obtained his world-known equation for time-dependent distribution function for dilute gas in non-equilibrium state in 1872. The Boltzmann equation provides a microscopic description of non-equilibrium processes in dilute gases as well as of gas transition to equilibrium state. Making use of the Boltzmann equation, Chapman and Enskog [9] derived the Navier–Stokes equation and obtained the expressions for dilute gas particles transport coefficients, which are characterized by pair interaction through short interaction forces. Even now, more than hundred years after Boltzmann derived his equation, the kinetic theory for dilute gases mainly studies stationary solutions to this equation for various initial and boundary conditions and different gas components. Fundamental results of the consistent derivation of the Boltzmann equation from the Liouville equation were obtained by Bogolubov in 1946 and later by Cohen, Green, Kirkwood, and Yvon [1,3,4,5,6]. The approach to the Boltzmann equation through the Liouville equation was found to be important for two reasons. First, it allowed to replace the Stosszahlansatz hypothesis of Boltzmann with more fundamental principle of the attenuation of the Bogolubov weakening correlations [2], and second, it also allowed to generalize the Boltzmann equation to dense gases. In the fundamental work of Bogolubov [2] there was also suggested and developed a new method for the study of the distribution function for gas, the so called method of generating functionals. By means of the generating functional there is taken down in the compact form the entire infinite hierarchy of the non-equilibrium equations for the distribution functions (Bogolubov’s hierarchy or BBGKY [1,6]), which under certain limitations on the functional allows for their various partial as well as approximate solutions. Solid explanation of the properties as well as possibilities of the method was later provided in the works of Bogolubov M.M. (Jr.) and co-workers [7,10,11,12] drawing upon the introduction of the so called quantum generating functional of the Bogolubov type and the study of its algebraic properties. Namely, it was found that the hierarchy of the Bogolubov equations in terms of the quantum generating functional realizes irreducible unitary representations of the quantum current Lie algebra which is a semi-direct product of the group of diffeomorphisms of a domain and the space of Schwartz functions on it. Within this approach all classic solutions are obtained, respectively, after moving to Wigner representations [3,10,13,14] for basic operators of the initial algebraic structure. For further analysis of the Bogolubov functional equation and the respective variety of its solutions for the given many-particle dynamical system, we are going to provide below its consistent derivation within the framework of the algebraic Bogolubov approach (Bogolubov M.M. Jr.) and establish its Hamiltonianity with respect to the special Lie–Poisson bracket on the orbits of the co-adjoined representation of the Wigner Lie algebra of quantum operators of the obeservable quanitites. We study in detail a special class of dynamical systems of Boltzmann–Bogolubov and Boltzmann–Vlasov type on infinite dimensional functional manifolds modeling kinetic processes in many-particle media. We analyzed an interesting example of Vlasov type kinetic equations generated by a quantum-mechanical model of spinless particles with delta-type interaction, having applications for describing so called Benney-type hydrodynamical particle flows. Based on the algebraic properties of the canonical quantum symmetry current algebra and its functional representations, devised before in [15], we succeeded in dual analysis of the infinite Bogolubov hierarchy of many-particle distribution functions and their Hamiltonian structure. Moreover, we proposed a new approach to invariant reduction of the Bogolubov hierarchy on a suitably chosen invariant subspace and deduced the related modified Boltzmann–Bogolubov kinetic equations on a finite set of multi-particle distribution functions. There are also presented results of application of devised methods to describing kinetic properties of a many-particle system with an adsorbent surface, in particular, there is derived the corresponding kinetic equation for the occupation density distribution function.
2. Kinetic Equations: Introductory Quantum-Mechanical Example
2.1. The Quantum Many-Particle Hamiltonian and the Related Quasi-Classical Averaging
It is well known [16,17] that the classical Boltzmann equation under no correlation condition describes long waves in a dense gas with a short-range interaction potential. The same equation, which is called the Vlasov equation [18], is equivalent to the hydrodynamic equations for long waves in an ideal incompressible liquid with a free surface under gravity. It also quite easy to see that this equation in the classical “random phase” approximation reduces to the well-known nonlinear model in plasma physics. These equivalences for the kinetic and hydrodynamic equations can be used for studying dynamical chaotic behavior in many-particle systems and often accompanying it turbulence arising in both in gas and fluid flows. These aspects are very important as dynamical many-particle systems possess an important intrinsic property of particle motion in a liquid-convective mass transfer of particles in a fixed volume—which is known to always accompany a transition from laminar to turbulent flow and cause convective vortex wise motion. It is also important that the realistic models to possess an intrinsic so-called “dry” viscosity for the particle flows.
To take into account these phenomena, we will introduce a new generalized dynamical system for the flow of particles in a domain namely a Boltzmann–Bogolubov kinetic equation in the Vlasov approximation with no many-particle correlation, describing long waves in a dense gas of particles with a short-range interaction potential. We will also derive the associated Benney type system of spatial equations containing the convective terms in a form that is especially convenient for describing the turbulence phenomenon. Moreover, the mathematical model of interacting particles we analyzed is such that the associated Benney type system of equations appears to be Hamiltonian and reduces to an interesting related three-dimensional hydrodynamic type particle flow.
Let us consider a quantum dynamical system on consisting of identical spinless particles with the singular Hamiltonian operator
where is an external constant momentum vector and is a real parameter, ℏ is the Planck’s constant (divided by is the particle mass, and is the classical Dirac delta-function. Then, corresponding Wigner’s transformation [3] to a quasiclassical weak limit as yields where the classical Hamiltonian function has the form
Here, the are the coordinates of the particles on the axis The Heisenberg operator commutator for evolution of dynamical observables [3] becomes the standard canonical Hamiltonian bracket viz.
in accordance with the classical Born principle. Therefore, on the cotangent phase space the Hamiltonian equations take the following form:
where is an evolution parameter and
In view of the singularities in (2), the Equations (4) are in general not solvable for arbitrary Cauchy data and large Therefore, because of our “kinetic” interest in the motion of (4), we pass further to its statistical description [3,19,20], using the Boltzmann–Bogolubov distribution function defined by
Here, and is a solution of the Hamiltonian Equation (4). It is well known [3] that the distribution function (5) satisfies the standard Liouville–Hamilton equation
Now, we apply the averaging operator to the distribution function (5) assuming no many-particle correlation over all initial states of (6). The averaging operation on (6) results in the kinetic Boltzmann–Vlasov equation [3,19] of the form
where is the statistically averaged distribution function (5) and is a new “averaged” Poisson bracket on the infinite-dimensional functional space which for a pair of functionals has the form [10,17]:
and is called the canonical Lie–Poisson bracket [10,17,21,22]. The Hamiltonian in (7) is given by
and “” denotes here the standard Euler variational derivative on
To derive (8) let us consider the phase space endowed with the canonical Poisson bracket where are smooth functions on The space has the structure of a Lie algebra with respect to this bracket (8).
Let be the adjoint or dual of i.e., the space of continuous linear functionals on The space is a pre-Hilbert space with respect to the scalar product defined by
Moreover, the adjoint sdpace is a Hilbert space, on which the above scalar product is invariant with respect to the Poisson bracket in the sense that
for all This structure enables us to determine the map by means of the formula for arbitrary Consequently, is here completely equivalent to the variational Euler derivative on the space of local functionals at point
The canonical Hamiltonian structure on the manifold can now be expressed via the well-known Lie–Poisson formula [10,17,21,22,23]
which, obviously, coincides with (8). To reveal the essence of the formula (7) we consider a coadjoint action of the Lie algebra on suitably generating a flow where is a real evolution parameter and is the flow generator at Then, owing to the invariance of the scalar product on the above vector field is equivalent to the following commutator representation on which in turn is equivalent to (8) after an identification
One easily observes that the Hamiltonian function H given by (9) is a conservation law for the Boltzmann–Vlasov system (7), i.e., for all Apart from this conservation law, the dynamical system (7) possesses the following additional invariant functionals on
where N is the number of particles and is the total particle momentum of the system.
2.2. Boltzmann Equation, the Associated Momentum Problem and Related Hydrodynamic Type Particle Flow
Below, we shall show that the Boltzmann–Vlasov system (7) with Hamiltonian (9) can be represented in the equivalent commutator form
where and possesses (with respect to the Lie–Poisson bracket) additional conservation laws, important for analysis its exact solutions [7,24].
The exact form of the Boltzmann–Vlasov Equation (11) is
where the momentum functionals are defined as follows:
for all and In momentum terms (13), the Hamiltonian (9) as a functional takes the form ∖ with the Lie–Poisson bracket (8) on the manifold being given by the expression [16,17,23,25]:
where is a skew-symmetric matrix operator on and is the standard inner product on the space of real square-summable sequences.
The dynamical system for the momentum functions corresponding to (12) is
where and are some constant parameters. The Equations (15) are called the generalized Benney type momentum system. In particular, for and we obtain the following from (15):
It is interesting to remark here that the simplest substitution in (16), responsible for the hydrodynamic representation of the averaged distribution function (6), we obtain the following new nonlinear Benney type system of equations:
where are particle velocity and density functions, owing to the natural physical identifications of our particle system as a suitable hydrodynamical flow in
Below we develop the classical Bogolubov approach to deriving kinetic equations for many-particle system, based on the fundamental quantum current algebra symmetry and its functional representations. The latter makes it possible to present a new description of the infinite hierarchy of distribution functions and construct the corresponding correctly decoupled infinite systems of kinetic equations for distribution functions.
The first draft [15] of this review was initiated and written jointly with our colleague and talanetd university teacher Prof. Lev I. Ivankiv, who recently passed away. The further work on the review was actively continued jointly with Prof. Valeriy H. Samoilenko and Dr. Yarema A. Prykarpatsky, whose impact in developing the Lev I. Ivankiv’s ideas appeared both essential and decisive while preparing a final version of the manuscript.
3. The Bogolubov Generating Functional in Non-Equilibrium Statistical Mechanics and Its Wigner Quasi-Classical Representation
3.1. The Current Lie Algebra Representation
Let us be given the Hilbert space of the states in the non-equilibrium quantum mechanics. There are defined field annihilation operator and creation operator which satisfy the commutation relationships of the bose- and fermi-type:
As a basic algebra [7,13,14,26,27,28,29] of the observed quantities, which describes the interaction of the particles in system, so called the current Lie-algebra is chosen. To construct it let us introduce the following basic operator quantities:
is the operator of the density of the particles;
is the operator of the particle flow density in the point It is easy to check that operators
where are rapidly decreasing functions of the Schwartz-type, is a scalar product in , which satisfy the following commutation relationships:
for all Current Lie algebra (22) is a basic object in the algebraic approach to the theory of the Bogolubov’s quantum generating functional. By the general physics principle any observable quantity belongs to the generalized universal enveloping algebra generated [30] by the basis current algebra (22). It is obvious, that operators (21) are self-adjoint in that is but in general case they can be unbounded, that is why it is natural to deal with the elements and which are defined as and generate group with the following composition rules:
for all and where is a parameter. Group G (23) is a semi-direct product where is a diffeomorphisms group of the domain The group rule, according to (23), has the following form:
where is an arbitrary element of the current group. The diffeomorphisms group in G as a topological space is an addition of the metrized locally linear connected (but not locally compact) subgroup of the smooth diffeomorphisms of the domain with the compact supports and standard group operation with composition of mappings.
It is well known [7] that different unitary representations of the current algebra describe different many-particle physical systems. For example, system of the N identical Fermi-particles and system of identical Bose-particles correspond to two unitary nonequivalent representations of this group. Since the group G is infinitely parametric, than its different possible unitary representations describe wide spectrum of the physics problems [7,30].
The Hilbert space for every irreducible unitary representation of the current group is unitary equivalent [7] to the Hilbert space
where is a cylindrical measure on the space of the continuous real linear functionals (distributions) on [31,32], are marked by the index complex linear spaces. In physics application it is frequently put , then is a space of quadratically integrable functions on with measure
Let us now take the arbitrary element Then the group action on this element has the following representation:
where
for all For the Radon-Nikodym derivative to exist in (26) the measure on should be quasi-invariant [13,14,31,33] with respect to the group , that is for any measurable set and arbitrary measure iff .
The representation (26), which corresponds to the quantum-chemical system identical particles, possesses measure , supported on the Dirac delta-function, i.e., on the functionals
with the measure
where and is a symmetrical or anti-symmetrical wave function of the base state of the N-particle dynamical systems. The following equalities hold:
and
where From (30) and (26) we can find the following relationships:
where we put for all in the case of Bose statistics,
Let us consider the representation of the current group limited on the Abel subgroup Then the corresponding Bogolubov-type generation functional [7] can be defined in the form
where cyclic vector of the representation is normed in as The generation functional (32) has wide use in the case of the representation of the current Lie algebra (22), which corresponds to the stationary (equilibrium) statistical state of the original many-particle dynamical system [7] and satisfy the following functional Bogolubov-type equation [34]:
Here, is the so-called characteristic operator of the representation , defined by the following operator relationship:
where and
are the elements of the enveloping algebra In the case of equilibrium statistical system state at inverse temperature the operator was first built by N. Bogolubov [34] by means of indirect method:
where is a standard normal operator ordering [3]:
where is arbitrary and for is a potential of two-particle interaction in the dynamical system. Taking into account, that
are Bogolubov’s n-particle distribution functions [34], from (33) it is easy to obtain unlimited hierarchy of the Bogolubov’s equations for the function (38), whose solutions are important for the physics applications.
As it was found in [34], the functional Equation (33) does not have a unique solution, that is why there posed the problem of choosing the solution with physical sense. This problem is solved in [7] by means of the functional representation operators of the Bloch equation in form of the additional compatible with (33) functional equation on Bogolubov’s functional
In the case of non-stationary (non-equilibrium) states of the many-particle dynamical systems the Bogolubov’s generating functional (32) doesn’t possess all needed information. We introduce the following Bogolubov’s type generating functional:
Here, is a cyclic vector of the representation of the current group G, which satisfies the following conditions:
where operator is an operator of the time inversion, and are arbitrary.
In N-particle representation of the Lie-algebra (30), the functional (39) has the following form:
where and is a cyclic state. The operator acts on any function by the rule:
where is a diffeomorphism corresponding to the vector field that is where For the expression (40) becomes
where for all Bogolubov’s quantum distribution functions [3] are
It is obvious that
where
To proceed with the further study of the classical distribution functions of the many-particle dynamical system (that is, and the Planck constant , let us introduce the following quantized Wigner operator , according to the works in [1,5,11,35]:
where ). Performing transformation (44) in the expression (39), we can find, that
where f From the expression (45) it also follows that
where is the corresponding Gibbs statistical operator. The corresponding quantum current Lie algebra transforms into the abelian Lie algebra of the operator functionals in a weak functional sense. This property will be used in the next sections.
3.2. The Bogolubov’s Functional Equations in Non-Equilibrium Statistical Mechanics
Let us be given the quantum dynamical system of the many identical particles with the average density and in Van Hove’s sense [5,6]. Then, according to [7,13,14], the Hamiltonian operator in the second quantization representation [3] is given by the expression
where is translationary invariant potential of the interparticle interaction, is a mass of one particle. In terms of operators of the current Lie algebra (22), the operator (47) can be rewritten [7,13,14] as
where the operator is given by the expression (44). Then, we can find the expression for the Wigner representation (44) for the Hamiltonian operator (47):
where and are the standard volume measures in According to the Heisenberg’s principle [3], the evolution equation by the variable for the arbitrary operator for the observable quantity is
where is a usual operator commutator. Following [3], it is easy to state, that for in the weak sense the following theorem is true.
Theorem 1.
Let us is an algebra of the self-adjoint operators with in the Wigner representation. Then operator bracket on the algebra in the weak sense is equivalent to
where is a standard canonical Poisson bracket on the phase space of particles.
The statement (51) could be proved by means of the next general Bohr–Dirac correspondence principle in the quasi-classical approach:
where N is a maximal number of the particle in system and are operators in N-particle Hilbert space representation
Corollary 1.
Algebra of the operators of the observable quantities for allows “hierarchical” representation
along with Lie bracket which is inducted by the bracket (51):
where in the Wigner representation and the following expansions hold
Let us consider the following linear mapping where
and the Lie bracket is defined in and the corresponding Lie bracket (51) in Let us consider the dual to (56) mapping where
Here, is statistic operator of the initial dynamical system (49), which satisfy the Heisenberg–Liouville equation
for all When the expression (58), according to (52), transforms into quasi-classical Liouville equation in the Wigner representation.
It is easy to check, that for element the expression
defines the representation on the space of the distribution functions
where and for any
Let be linear functionals on then on there is defined standard [7] Lie–Poisson bracket via the rule
where are such that In the same way the dual Lie–Poisson bracket is defined on the set of functionals over the adjoint space (57)
where
Definition 1.
It is said, that mapping of the Lie algebras is canonical (or Poissonian [7]), if for all and the following equality holds:
where
From the reasoning above, we can formulate the following proposition.
Proposition 1.
Let A and are two arbitrary Lie algebras, and is a linear mapping. Then, dual mapping is canonical iff is Lie algebras homomorphism.
As a consequence of the statement above, one derives the next theorem.
Theorem 2.
Dual mapping , which was built by means of the hierarchical Lie algebra of the operators is canonical.
Let us consider the generating functional (46) in Wigner representation and apply the developed above algebraic technique to the calculation of the following quantity:
when and
From (66) and Theorem 2, we immediately obtain that
where and is arbitrary.
Thus, the following theorem is stated.
Theorem 3.
Using Equation (68) and formulae (51) and (54), we finally get the following non-equilibrium functional Bogolubov’s equation [2]:
where for any according to (37)
and, by definition, denotes the standard canonical Poisson bracket on the phase space for all
Taking into account, that for functional there exists the unlimited expansion (45):
from (69) we obtain the kinetic equations for the hierarchy of the Bogolubov’s distribution functions [2]:
where are the coefficients of the n -particle cluster in is its corresponding energy:
Thus, the problem of the construction of the kinetic theory by Bogolubov reduced to the finding the special solutions of the unlimited hierarchy of the Equations (72), where the selection criterion is based on the Bogolubov’s fundamental weakening correlation principle:
where is a distance between two clusters with and numbers of the particles.
If there exists a special solution of the hierarchy (67) in the functional form
for all and then the corresponding equation for one-particle distribution function of the system in the external field is the following:
where is the so-called “collision integral” [1,2,3,4,5] and is called the kinetic Boltzmann equation [1,3]. Below we will focus on the such special solutions of the Bogolubov’s hierarchy of the Equations (72), using the developed above algebraic method of the Bogolubov’s generating functional.
4. Kinetic Boltzmann Equation in Non-Equilibrium Statistical Mechanics within Bogolubov’s Approach
4.1. Main Bogolubov Functional Equation and Its Solutions
Let us consider the Bogolubov’s functional Equation (69) with the given initial data
where for all
is a solution of the Heisenberg evolution equation
for the statistical Gibbs operator with
When in the Wigner representation the expression (78), as an explicit solution of the (79), allows the following expansion:
where we marked
Operator in (81) is called “cluster operator” and allows the next expansion into the unlimited series:
where the functions can be defined uniquely form the representation (81) under condition that Gibbs operator is defined explicitly in the Wigner representation.
Thus, from (80)–(82) we obtain the following expressions for the Bogolubov’s generating functional
where is a generating functional if the initial dynamical system of the particles under absent of interaction, that is
Thus, according to (83) and (85), we find that
is a solution of the Bogolubov’s functional Equation (77), where
for all To specify the form of the operators (87) we note, that operator for all satisfies under the following differential evolution relationship:
where all operators assumed to be given in the Wigner representation. Expanding operator into the sum of n-particles components, , we find
and there is mutually unambiguous correspondence [3,7] between coefficient functions in (89) and coefficient functions in the expansion (82)
Here, is an arbitrary partition of the symmetry group of all permutations of the set of numbers on the subsets which are not intersect, that is and and are the corresponding to this partition coefficient functions. In particular,
and so on. Thus, on the base of defined operator series (82) or (89) the problem of the explicit calculations of the distribution functions become very simple. Below we will analyze these series by means of the language of the Bogolubov’s generating functional using the Bogolubov’s functional hypothesis [1,2,3,4,5].
4.2. Bogolubov–Boltzmann Kinetic Equation in the Frame of Functional Hypothesis
The generating functional, as it was stated above, is given by the expression
Here, is a generating functional of the system of non-interacting particles, which is equal to the expression (85) when From (91) follows, that for all for the n-particle distribution function the general functional relationship holds:
Respectively, the generating functional (91) satisfies, according to (68) when , the following dynamic equation:
Let us put where and
Then from (93) we also obtain that
for all Then Equation (95) can be rewritten in the following way:
where, by definition, and
is the Vlasov-type Hamiltonian of the self-consistent particles interaction. Let us define the following mapping on the phase space of particles:
where for all
It easy to see, that system of Equations (99) gives the exact solution [32] for the dual Equation (94) in the form of the sum of -functions of particles:
where are the coordinates of the cluster. Using (98) from (96) we obtain, that for all
where we denoted
Integrating the Equation (101) in limits we obtain, that
We should also note here, that due to the Bogolubov’s principle of correlations attenuation (74) and using (85) the first item in (103) can be represented in the form
Applying to the expression (103) the different variants of the successive approximations method [1,2,3,4,5], we can get the generating functional in explicit form and then, using formula
for all obtain distribution function for any order of perturbation theory. In particular, choosing expansion by the particle density in container as a small parameter, it is easy to get modified kinetic Bogolubov–Boltzmann equation for one-particle distribution function :
where the function is defined according to (103) and (104) by the following expression:
for Taking into account, that Poisson bracket is invariant with respect to the mappings from (107) it is easy to find, that
where is a parameter of the axis in cylindrical coordination system which directed along the vector and with beginning at the point After substituting (108) into (106) we can get kinetic Bogolubov–Boltzmann equation [1,2,3,4,5] in form of (76) with the explicitly defined collision integral obtained from (108) via integration by Choosing in (104) other approximations of the generating functional one can find other forms of Bogolubov–Boltzmann kinetic Equation (76).
We can also make a remark concerning the nature of the operator-functional expression (87) or (82). Namely, it is easy to see that generating functional allows the following operator-functional representation for all
Comparing the expressions (109) and (83), we find that, for arbitrary ,
as the functional is arbitrary. It is easy to see from (110), that operator is not poly-local with respect to the functional derivatives which corresponds to the singularity in the operator expansion (82). Thus, using the expression (109), arbitrariness of the initial state and Bogolubov’s attenuation correlation condition gives a possibility to find many types of the solutions via the method of successive approximations, which follows from (109) and Bogolubov’s functional hypothesis.
5. Kinetic Equations, Their Algebraic Structure and Invariant Reductions
5.1. Lie-Algebraic Setting
It is well known that the classical Bogolubov–Boltzmann kinetic equations under the condition of many-particle correlations [1,3,4,5,6,9,19,32,34,36,37,38] at weak short range interaction potentials describe long waves in a dense gas medium. The same equation, called the Vlasov one, as it was shown by N. Bogolubov [32], describes also exact microscopic solutions of the infinite Bogolubov chain [34] for the many-particle distribution functions, which was widely studied making use of both classical approaches in [3,19,20,38,39,40,41,42,43,44,45,46,47,48] and in [10,11,15,49,50,51,52,53,54], making use of the generating Bogolubov functional method and the related quantum current algebra representations.
A.A. Vlasov proposed his kinetic equation [18] for electron-ion plasma, based on general physical reasonings, that in contrast to the short range interaction forces between neutral gas atoms, interaction forces between charged particles slowly decrease with distance, and therefore the motion of each such particle is determined not only by its pair-wise interaction with either particle, yet also by the interaction with the whole ensemble of charged particles. In this case the Bogolubov equation for distribution functions in a domain
where is the temporal evolution parameter, denotes the canonical Poisson bracket [3,21,22] on the product and is an interparticle interaction potential, reduces to the Vlasov equation if to put in (111)
that is to assume that the two-particle correlation function [19,20,36,38] vanishes:
for all and Then, one easily obtains from (111) that
for all and Remark here that the Equation (114) is reversible under the time reflection thus it is obvious that it can not describe thermodynamically stable limiting states of the particle system in contrast to the classical Bogolubov–Boltzmann kinetic equations [1,3,6,10,15,19,34,38], being a priori time non-reversible owing to the choice of boundary conditions in the correlation weakening form. This means that in spite of the Hamiltonicity of the Bogolubov chain for the distribution functions, the Bogolubov–Boltzmann equation a priori is not reversible. It is also evident that the condition (113) does not break the Hamiltonicity—the Equation (114) is Hamiltonian with respect to the following Lie–Poisson–Vlasov bracket:
where respectively are smooth functionals on the functional manifold consisting of functions fast decreasing at the boundary of the domain The statement above easily ensues from the following proposition.
Proposition 2.
Let denote a set of many-particle distribution functions. Then the classical Bogolubov–Poisson bracket [10,11,34,44] on the functional space reduces invariantly on the subspace to the Lie–Poisson–Vlasov bracket (115).
This proposition and its different consequences will be analyzed in more detail in sections to follow below.
5.2. The Lie–Poisson–Vlasov Bracket
The bracket expression (115) allows a slightly different Lie-algebraic interpretation, based on considering the functional space as a Poissonian manifold, related with the canonical symplectic structure on the diffeomorphism group of the domain first described [55,56] still in 1887 by Sophus Lie. Namely, the following classical theorem holds.
Theorem 4.
The Lie–Poisson bracket at point on the co-adjoint space is equal to the expression
for any smooth right-invariant functionals
Proof.
By classical definition [21,22,55,56,57] of the Poisson bracket of smooth functions on the symplectic space it is easy to calculate that
where Since the expressions and owing the right-invariance of the vector fields the Poisson bracket (117) transforms into
for all and any The Poisson bracket (118) is easily generalized to
for any smooth functionals finishing the proof. □
Concerning our special problem of describing evolution equations for one-particle distribution functions, we will consider the one particle cotangent space over a domain and the canonical Poisson bracket on for which, by definition, for any
where Denote now by the related functional Lie algebra and its adjoint space with respect to the standard bilinear symmetric form on the product where
The constructed Lie algebra with respect to the bilinear symmetric form (121) proves to be metrized, that is and
for any and is a smooth functional on its gradient at point is naturally defined via the limiting expression
for arbitrary element Define now the Poisson structure by means of the standard Lie–Poisson [7,21,22,37,55,56,58] expression:
for arbitrary functionals It is evident that the expression (124) identically coincides with the Poisson bracket (115).
Consider a functional and the related co-adjoint action of the element at a fixed element
where is the corresponding evolution parameter. It is easy observe that
is a Hamiltonian equation with the functional taken as its Hamiltonian, being simultaneously equivalent to the following canonical Hamiltonian flow:
if to choose as a Hamiltonian the following functional
where is a two-particle interaction potential, It is easy to observe here that the Hamiltonian (128) is obtained from the corresponding classical Bogolubov Hamiltonian expression
where denotes an infinite vector from the space of multiparticle distribution functions, and if to impose on it the constraint (112). Thus we have stated the following proposition.
5.3. The Boltzmann–Vlasov Equation, Its Microscopic Exact Solutions and Functional Properties
Proposition 2, stated above, claims that the Boltzmann–Vlasov Equation (114) is a suitable reduction of the whole Bogolubov chain upon the invariant functional subspace Moreover, this invariance in no way should be compatible a priori [10,11,15,32,45,46,50] with the other kinetic equations from the Bogolubov chain, and can be even contradictory. Nonetheless, as it was stated [32] by N. Bogolubov, namely owing to this invariance of the subspace the Boltzmann–Vlasov Equation (114) in the case of the Boltzmann–Enskog hard sphere approximation of the interparticle potential possesses exact microscopical solutions which are compatible with the whole hierarchy of the Bogolubob kinetic equations. The latter is, obviously, equivalent to its Hamiltonicity on the manifold with respect to the Lie–Poisson bracket (124). The Boltzmann–Enskog kinetic equation [6,20,32,36,38] equals
where a particle diameter, —a unit vector, and, by definition, for all satisfying the condition The Equation (130) easily reduces to the Vlasov–Enskog equation
for all , owing to its Hamiltonicity on the space If, in addition, there exists a nontrivial interparticle potential, the equation above is naturally generalized to the kinetic equation
which remains to be Hamiltonian on and possesses, in particular, the following exact singular solution:
where - phase space coordinates in of interacting particles in the domain Specified above the Hamiltonicity problem and the existence of exact solutions to the Botzmann–Vlasov kinetic Equation (132) is deeply related to that of describing correlation functions [19,20,38], suitably breaking the infinite Bogolubov chain [10,19,34,38,52,53] of many-particle distribution functions. Namely, if to introduce manyparticle correlation functions [19,20,38] for related Bogolubov distribution functions as
where then the Vlasov Equation (132) is obtained from the Bogolubov hierarchy at and for all
As it was mentioned above, the constraint imposed on the infinite Bogolubov hierarchy is compatible with its Hamiltonicity. Yet in many practical cases this closedness procedure by means of imposing the conditions like
for all at some fixed gives rise to some serious dynamical problems related with its mathematical correctness. Namely, if to close this way the infinite Bogolubov chain of kinetic equations on manyparticle distribution functions, one easily checks that the imposed constraint (135) does not persists in time subject to the evolution of the distribution functions This means that these naively reduced kinetic equations are written down somehow incorrectly, as the reduced functional submanifold should remain invariant in time. To dissolve this problem we are forced to consider the whole Bogolubov hierarchy of kinetic equations on multiparticle distribution functions as a Hamiltonian system on the functional manifold and correctly reduce it on the constructed above functional submanifold via the classical Dirac type [7,21,22,24,59] procedure. The kinetic equations obtained this way by means of the reduced Lie–Poisson–Bogolubov structure will evidently differ from those naively obtained by means of the direct substitution of the imposed constraint (135) into the Bogolubov chain of kinetic equations, and in due course will conserve the functional submanifold invariant.
5.4. The Invariant Reduction of the Bogolubov Distribution Functions Chain
Consider the constructed before Hamiltonian functional (129)
and calculate the evolution of the distribution functions vector under the simplest constraint (135) at that is
for all To perform this reduction on we need [7,24,59] to constraint the -extended Hamiltonian expression
for some smooth function and next to determine it from the submanifold invariance condition
for all and To calculate effectively the condition (139) let us first calculate the evolutions for distribution functions and
and
which can be rewritten equivalently as follows:
and
Having now substituted temporal derivatives (142) and (143) into the equality (139) in their explicit form, one obtains the following functional relationship:
which is satisfied if
for all Taking into account the result (145), one easily obtains from the Equation (142) the invariantly reduced on the submanifold kinetic equation on the one-particle distribution function:
which can be rewritten in the following compact form:
where we put, by definition,
The kinetic Equation (146) naturally coincides exactly with that obtained before from the naively reduced evolution equation
on the submanifold as it is globally invariant [10,44] with respect to the classical Lie–Poisson–Bogolubov structure on The same way as above one can explicitly construct the system of invariantly reduced kinetic equations
on the submanifold which already is not a priori globally invariant with respect to the Hamiltonian evolution flows on and whose detail structure and analysis are postponed to another place.
6. Kinetic Theory of the Many-Particle Systems and Adsorption Phenomenon
6.1. Boltzmann–Bogolubov Equation, Surface Peculiarities, and Collision Integral
Let us consider a one-component many-atoms dynamical system of the particles, which are contained in the bounded volume , where the density is considered small enough. It allows us to use the developed before the theorey of the Bogolubov–Boltzmann kinetic equations for the dilute gases.
The Hamilton function of our dynamical system we write down as
where is interparticle interaction potential, is a potential of the particle interaction with the domain walls, that is with it surface and is a general number of particles. We assume that potential in (151) has Van der Waals nature, possesses the area of attraction as well as area of repulsion. The surface potential is very important, because it provide the condition of particle systems limitation in the fixed volume It should be noted, that during analysis of particle interaction with the walls of volume that is with the surface the different non-potential models of the particle interaction with the surface are used.
Small particle density in the volume means that where is an effective volume of the one particle. For example, for the air under the normal conditions , that is . Under such conditions we can assume that gas particles in the volume are moving most of the time freely, performing only frequent collision among each others.
Using the results of the previous section, namely the Equation (106) under condition (108), we can write down the following kinetic Bogolubov–Boltzmann Equation (76) for one-particle distribution function.
where the collision integrals and in (152) are given by the following explicit expressions:
where is infinitesimal element of the surface measure . The first item in (153) corresponds to interparticle collision in the volume , the second item to the collision with the surface of the container is a standard Heaviside function, ( , ), is a kernel of the probabilistic distribution of the particles under the interaction with the surface The point nature of the process is reflected by the Dirac -function in (153). In the case of conservation on the number of particles in the container the kernel should satisfy the natural condition:
for all under condition The condition (154) means, that the walls of the container are not adsorbing the particles and the probability of particle reflection from the wall is equal to is a normal to the surface in the point It is obvious, that under these limitations on the surface the velocity with which in the given point the particles leave the surface, is equal the velocity of the collide with the surface under the given momentum of the scattering that is
for all Here, we will not concretize the explicit structure of the kernel because of its strong dependency on the choice of interaction potential in the Hamiltonian (151). It will be the object of a further more detail study.
6.2. The Interactive Surface and Boundary Conditions
As it was noted above, the distribution function , as a solution of the Bogolubov-Boltzmann Equation (153), should be equal to zero in the area that is beyond the container which contains the particles. This condition is realized by means of the following representation for the distribution function:
where and is characteristic function of the surface that is for and for Substituting expression (156) into (151) and (152) we can find that for all
where and From the last equality we conclude, that for all
as a corollary of the dynamic equilibriumcondition (155). Thus, we obtained the necessary set of the boundary conditions for the distribution function for on the surface These boundary conditions should be taken into account during solution kinetic Bogloubov-Boltzmann Equation (157) in the container
6.3. Adsorption Kinetics Equations
Let us consider similar to the previous many-particle system in the volume where the part of the surface has the adsorbing properties, that is the conditions (153,154) are violated for It leads to accumulation of the adsorbed particles on the surface which causes its dynamic equilibrium with the gas particles from the volume for . In this case, the mechanism of the adsorption by the surface centers on needs to be additionally clarified. Let us represent the surface as a discretely distributed set of the active adsorption centers with the potential energy of the activation and the highlighted momenta where It means, that the surface one can imagine as a ”spiky” lattice of the positively (inside ) oriented fixed impulse centers of adsorption. During particle ”capturing” with the momentum by the surface its total momentum becomes zero and its corresponding ”activation” energy
Thus, the basic information about adsorption process of the particles on the surface is contained in the kernel of the collision integral because on the other part of the surface adsorption does not occur. Taking this into account, we need to change the kinetic Equation (152) for this case, where, in particular, we need take into consideration the particle interactions in the volume with the adsorbed particles on the surface and also the process of the adsorption center filling, which reduce the probability of its filling with time.
The kernel in (160) takes into account the nature of the gas particle collision in the volume with the adsorbed centers on the surface . Taking into consideration that the representation (156) holds for the distribution function as a solution of the Equation (159), we get, that in the case for all
in the case and
in the case the quantity
is a velocity of the particles runoff from the -part of the surface , which is filled with the adsorbed particles; in the case and the quantity
is a velocity of the adsorption of gas particles on the -center of the free part of the surface . Here , and we denoted the corresponding kernels in the collision integrals via and . It is obvious that kernel corresponds to the collision integral of the gas particles on the similar particle but in the fixed form on the surface , whereas the kernel defined by nature of the adsorption centers on the part of the surface
We will use the obtained expressions (161)–(164) to find the integral velocity of the filling the adsorption centers on the surface . Namely, it is easy to observe, that the total number of the particles on the surface satisfies the following differential relationship
which according with (161)–(164) is equivalent to the integral relationship in the form
where for all
The obtained expression needs to be clarified, using the nature of adsorption centers distribution on the surface and fact, that the part of the surface which is filled by the adsorbed particles, contains them in the number of Thus, if the function of independent distribution of the adsorption centers on the surface is given, then the integral Equation (166) can be rewritten as
where we denoted
The system of the Equations (168) and (169) should be completed with one more Equation (157)
for values and the condition
on the distribution function in the volume in the vicinity of the element The obtained system of the integral-differential Equations (168)–(171) is closed and gives the solution of the problem of construction the kinetic Bogolubov–Boltzmann equations in the bounded volume with the surface peculiarities of it boundary
6.4. Kernels of the Collision Integrals and Their Structure
As it was mentioned above, during the study of the adsorption processes on the surface of the volume of the many-particle dynamical system the kernels of the collision integrals of the particle’s collision with particles with the surface and adsorbed on the surface particles play the main role. Let us consider the case of collision integral that is collision of the particles from the volume with the adsorbed particles on the the surface It is obvious that, in general case,
where is a corresponding collision integral of the particles from the volume with the free from the adsorbed particles surface , and for all ,
Let us consider the collision integral based on the general expression for the collision integral in the volume under the condition, that the particle with the phase coordinate scatters on the adsorbed particle in the point Moreover, if the phase coordinate of the scattered particle on the surface is equal to , then the collision momenta of the two particles satisfies the relationships [2,6]
where is a unit vector along the line of the centers of the interacting particles with the beginning in the point is a momentum of the particle in the volume before the collision, is a momentum after the collision, is an own momentum of the adsorbed in the node particle, which satisfies the natural condition of the particle not leaving the surface In the opposite case, when the adsorbed particle leaves the surface
Let us write down the general expression for the collision integral
Let us put
as it was done in [2], where, by definition,
is a generator of the canonical mappings group of the two-particle problem with the interaction potential, is a corresponding generator of the canonical transformations group of the non-interaction two-particle problem, and
is a probability scattering functions on the adsorbed node after the particles collision,
is a probability scattering functions on the adsorbed node before the particles collision. The function in the most practical cases can be given as
where is a normalizing constant of the density of the scattering centers states of the adsorbed particles on the surface is their effective ”surface particle”mass, and Thus, according to (176)–(179), the collision integral (175) is given by the expression (173), where
Here, one should also note that when the condition for some pairs is fulfilled, then after collision with the gas particle, which is adsorbed on the node the particle became free, that is the particle returns from the surface to the volume Thus, as it was noted before, the kernel makes it possible to describe the process of the adsorbed particles releasing on the surface We do not stop here more on this in details and refer the reader to the explicit expressions (163) and (164).
By means of the similar to the described above method the problem of the calculation of the kernels of the scattering integrals on the surface and can be solved. In particular, for the description of the elastic collision with the inertial adsorbing centers we can get the following explicit expressions
where are the corresponding normalizing constants, are the inertial ”masses”of the adsorbing centers on the surface Thereby, we constructed concerted macroscopic theory of the kinetic processes in the many-particle dynamical systems in the bounded volume with taken into account adsorption phenomena, which are caused by the surface peculiarities.
Author Contributions
The main review idea and feature topics were conceived and suggested by L.I.I. and A.K.P., the first three Sections were prepared by Y.A.P. and V.H.S., the last sections were written jointly by A.K.P. and V.H.S. All authors have read and agreed to the published version of the manuscript.
Funding
This research received no external funding.
Institutional Review Board Statement
No humans and animals were involved into the research.
Informed Consent Statement
No humans and animals were involved into the research.
Data Availability Statement
There were used no supporting publicly archived datasets.
Acknowledgments
The deep Author ’s acknowledgements belong to the bright memory of recently passed away talented ukrainian physicist Lev Ivankiv with whom there were obtained most of the results of this work. Authors also would like to convey their warm thanks to Gerald A. Goldin for many discussions of the work and instrumental help in editing a manuscript during the XXVIII International Workshop on “Geometry in Physics”, held on 30.06.-07.07.2019 in Białowieża, Poland. They also are cordially appreciated to Joel Lebowitz, Denis Blackmore and Nikolai N. Bogolubov (Jr.) for instructive discussions, useful comments and remarks on the work. A special author’s appreciation belongs to Joel Lebowitz for the invitation to take part in the 121-st Statistical Mechanics Conference, held May 12-14, 2019 in the Rutgers University, New Brunswick, NJ, USA. Personal A.P.’s acknowledgement belongs to the Department of Physics, Mathematics and Computer Science of the Cracov University of Technology for a local research grant F-2/370/2018/DS.
Conflicts of Interest
The authors declare no conflict of interest.
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