Diffusion equation in the theory of vibrational relaxation of diatomic molecules

A kinetic equation is obtained for the distribution function of anharmonic oscillators with respect to the vibrational energy; it enables one in the diffusion approximation to describe the vibrational relaxation of diatomic molecules in a medium of inert gas when there is a weak interaction between the oscillators and a thermal bath. The main difference from the equation for harmonic oscillators is in the appearance in the diffusion coefficient of an adiabaticity function that characterizes the variation of the adiabaticity factor because of the anharmoni-city of the vibrations. It follows from the form of this function that the greatest difference between the relaxation of anharmonic and harmonic oscillators is to be expected in the case of adiabatic interaction of oscillators with particles of the inert gas.     

On the theory of vibrational relaxation of diatomic molecules

The relaxation of diatomic molecules (harmonic oscillators) in a relatively light inert gas, which plays the part of a thermostat, is considered within the framework of classical mechanics. The gas-kinetic equation for the distribution function of diatomic molecules is approximated by the Fokker-Planck equation in the space of the energies of translational, rotational and vibrational motions on the assumption of strong nonadiabaticity of the collisions. In the approximation discussed, relaxation processes with different degrees of freedom develop independently, although the characteristic times of these processes are quantities of the same order. The vibrational relaxation time, expressed in terms of the gas-kinetic integral ^*(1,1) (T*), is obtained.     

Kinetic equations for vibrational relaxation in a mixture of polyatomic gases

Kinetic equations are derived for the relaxation of the vibrational energy in a mixture of polyatomic gases, which are ones with molecules simulated by harmonic oscillators. The most general case is envisaged, where the energy relaxation occurs not only via vibrational-translational transitions but also via multiquantum vibrational exchange involving an arbitrary number of vibrational modes. The analysis also incorporates the possible degeneracy of each mode when the molecules colliding are the same. An expression is derived that extends previous results [1–6] and that relates the vibrational temperatures in the case of quasiequilibrium. Equations are derived for the vibrational relaxation for the CO₂-N₂ case.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 6, pp. 29–37, November–December, 1972.We are indebted to L. A. Shelepin for valuable discussions on the results.     

Fractional relaxation processes and fractional rheological models for the description of a class of viscoelastic materials

Following the modelling of Zener, we establish a connection between the fractional Fokker-Planck equation and the anomalous relaxation dynamics of a class of viscoelastic materials which exhibit scale-free memory. On the basis of fractional relaxation, generalisations of the classical rheological model analogues are introduced, and applications to stress–strain relaxation in filled and unfilled polymeric materials are discussed. A possible generalisation of Reiner's Deborah number

is proposed for systems which exhibit a diverging characteristic relaxation time.     

Diffusion in pore fractals: A review of linear response models

A major aspect of describing transport in heterogeneous media has been that of relating effective diffusivities to the topological properties of the medium. While such effective transport coefficients may be useful for mass fractals or under steady state conditions, they are not adequate under transient conditions for self-similar pore fractal media. In porous formations without scale, diffusion is anomalous with the mean-squared displacement of a particle proportional to time raised to a fractional exponent less than unity. The objective of this review is to investigate the nature of the laws of diffusion in fractal media using the framework of linear response theory of nonequilibrium statistical mechanics. A Langevin/Fokker-Planck approach reveals that the particle diffusivity depends on its age defined as the time spent by the particle since its entry into the medium. An analysis via generalized hydrodynamics describes fractal diffusion with a frequency and wave number dependent diffusivity.     

Application of nonlinear hereditary strain theory to description of stress relaxation in metals,and conversion of relaxation data to creep

The possibility of describing relaxation and creep processes in metals and the possibility of direct conversion of data obtained in one type of tests to another, within the framework of the theory of hereditary creep based on the application of the Rabotnov nonlinear integral equation [1], are investigated.     

Saturation of absorption of the powerful radiation of a system of anharmonic oscillators

Recently, the theory of nonequilibrium systems simulated by a set of anharmonic oscillators has received significant development. The investigation of such kinds of systems is especially important in the study of problems associated with the stimulation of chemical reactions and the development of effective molecular lasers. The systematic analysis of the kinetics of anharmonic oscillators assumes the simultaneous solution of a large number of nonlinear equations describing the population balance of the vibrational levels. Realization of this approach is associated with cumbersome numerical calculations and does not permit obtaining a qualitative picture of the behavior of the system as a function of the different parameters (pressure, temperature, etc.). An approximate analytical theory has been formulated in [1, 2] which permits finding the distribution function over the vibrational states with the effects of anharmonicity taken into account. We will employ the approach developed in these papers to describe a system of anharmonic oscillators under conditions of powerful optical pumping. This problem was discussed in [3], where it was found that such a system changes into a saturation mode in the case of high pumping levels. The existence of this mode is explained by the fact that the maximum rate of energy input into a vibrational degree of freedom is determined by the rate of distribution of this energy over all the vibrational levels, i.e., by the constant of V—V-exchange. For sufficiently large pumpings the approximation of the Boltzmann distribution function adopted in [3] in connection with the calculation of the saturation parameters is too crude. The goal of this paper is to derive in explicit form expressions for the vibrational energy supply, the absorbed power, and so on, under saturation conditions without the use of the approximation indicated above [3].Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 5, pp. 10–15, September–October, 1978.     

Dispersion Relations for the Linearized Fokker-Planck Equation

We analyze the spectral properties and dispersion relations for the linearized Fokker-Planck operator in the case of hard potentials, as in Ellis & Pinsky's work [7] on the Boltzmann equation. Results similar to those in [7] are obtained for the Fokker-Planck operator although the presence of a diffusion operator instead of a multiplication operator introduces many additional technical difficulties. (Accepted December 7, 1995)     

Relaxation of anharmonic molecules

The inclusion of anharmonic effects is important in vibrational population inversions in CO-lasers [1, 2], in relaxation processes in jets [3], in thermal dissociation [1], in the kinetics of chemical reactions with high thresholds [4], etc. Usually these effects are studied by including anharmonic corrections to the kinetic constants in the discrete model of single-quantum transitions or in the diffusion approximation [1, 2]. In [5] a method was given of solving the relaxation equations fro arbitrary forms of the rate constants and the spectrum of the molecule. The method is valid when the ratio of the population densities of neighboring levels varies smoothly with quantum number. It was shown in [5] that this approximation can be used to construct analytical solutions for a wide class of problems. In the present paper the method of [5] is extended to the case of equations with variable coefficients. The properties of the solutions for VT-relaxation of anharmonic molecules are analyzed, and the inclusion of sources is considered. A simple method of taking into account multiple-quantum transitions is given, as well as an extension of the method to an arbitrary mixture of gases. The population densities are calculated and the possibility of using our solutions in relaxation gas dynamics is discussed.Translated from Zhurnal Prikladnoi Mekhaniki Tekhnicheskoi Fiziki, No. 3, pp. 22–31, May–June, 1986.     

Comparison of different models for non-equilibrium CO2 flows in a shock layer near a blunt body

The paper presents results of a numerical simulation of a supersonic two-dimensional (2D) viscous flow containing CO₂ molecules near a spacecraft entering the Mars atmosphere. The gas–dynamic equations in the shock layer are coupled to the equations of non-equilibrium vibrational and chemical kinetics in the five-component mixture CO₂/CO/O₂/C/O. Transport and relaxation processes in the flow are studied on the basis of the rigorous kinetic theory methods; the developed transport algorithms are incorporated in the numerical scheme. The influence of the vibrational excitation of CO₂ and chemical reactions on the gas flow parameters and heat transfer is analyzed. The obtained results are compared with those found using two simplified models based on the two-temperature and one-temperature vibrational distributions in CO₂. The accuracy of the simplified models and the limits of their validity within the shock layer are evaluated. The effect of bulk viscosity in a flow near a re-entry body is discussed. The role of different diffusion processes, chemical reactions, and surface catalytic properties in a flow of the considered mixture in the shock layer is estimated.     

Approximate statistical theory of a fluidized bed

Under the conditions of developed fluidization there are intensive fluctuations both in the fluidizing medium and in the dispersed solid phase. These motions have a decisive effect on the rheologlcal properties of the fluidized bed, and on the chemical reactions and transport processes taking place in it [1], Thus, for example, in the experiments of Wicke and Fetting [2], who investigated the heat transfer between a fluidized bed and the walls of a heated container, the effective heat transfer coefficient was found to be higher by an order of magnitude than the corresponding result for a fluidized bed held down by a wire grid so that the random motion of the solid phase was reduced. It is clear that the initial stage of any study of the structure of the fluidized bed as a whole, and of the subsequent development of any model, must involve an investigation of local structural properties, including the above fluctuations.The time variation of the individual particle velocities is due to two different causes. First, there is the interaction between the particles both through direct collisions and through the medium of the liquid phase, and, secondly, there is the interaction with the viscous fluid. These two factors are not independent, so that the set of fluidized particles has certain features characteristic for both a dense gas, with a potential intramolecular interaction, and a set of particles executing Brownian motion in a continuous medium.Any detailed statistical theory of a system of fluidized particles must be based on a representation of the random particle motions in the medium by a stochastic process with some definite properties (see, for example, [3–4]). Ideally, this theory should lead to the formulation of a transport equation which, in view of the above properties of the system, should have some of the features of both the usual Boltzman transport equation and the Fokker-Planck equation. The solution of this final equation is, of course, more difficult than the solution of the Boltzman or Fokker-Planck equations. Moreover, there is also the problem of applying this equation to different special cases. An alternative approach is to develop an approximate, but still sufficiently effective, theory of the local properties of the fluidized bed, which would combine relative simplicity in application with sufficient rigor and generality. This kind of theory is put forward in the present paper. The conclusions to which it leads are in good qualitative agreement with experiment.The author wishes to thank G. I. Barenblatt and the participants of his seminar for useful discussions.     

Calculation of the characteristics of a gas-dynamic laser

The dependence of the radiated power on the characteristics of optical cavities in the case of flow systems has been investigated in a number of papers [1–3], in which it is assumed that population inversion of the laser levels is obtained until entry into the cavity. The operation of a cavity is analyzed in [1] in the geometric-optical approximation with allowance for vibrational relaxation in the gas flow. A simplified system of relaxation equations is solved under steady-state lasing conditions and an expression derived for the laser output power on the assumption of constant temperature, density, and flow speed. The vibrational relaxation processes in the cavity itself are ignored in [2, 3]. It is shown in those studies that the solution has a singularity at the cavity input within the context of the model used. In the present article the performance characteristics of a CO₂-N₂-He gas-dynamic laser with a plane cavity are calculated. A set of equations describing the processes in the cavity is analyzed and solved numerically. Population inversion of the CO₂ laser levels is created by pre-expansion of the given mixture through a flat hyperbolic nozzle. The dependence of the output power on the reflectivities of the mirrors, the cavity length, the pressure, and the composition of the active gas medium is determined.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi FiziM, No. 5, pp. 33–40, September–October, 1972.     

The second initial-boundary value problem for a quasilinear parabolic equations with nonlinear boundary conditions

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｆａｓｔｄｉｆｆｕｓｉｏｎｅｑｕａｔｉｏｎｏｆｄｉｖｅｒｇｅｎｃｅｆｏｒｍａｓｕｔ =(ａ(ｕ)ｕｘ) ｘ ｂ(ｕ) ｘ ｃ(ｕ)　　 (ａ( 0 ) = ∞ ) ( 1 )ｈａｓｉｍｐｏｒｔａｎｔｐｈｙｓｉｃａｌｂａｃｋｇｒｏｕｎｄ ,ｓｕｃｈａｓ [1 ] .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｓｏｍｅｒｅｓｕｌｔｓａｂｏｕｔ ( 1 )ｈａｖｅｂｅｅｎｏｂｔａｉｎｅｄ .Ｆｏｒｅｘａｍｐｌｅ ,[2 ] ,[3]ｒｅｓｐｅｃｔｉｖｅｌｙｄｉｓｃｕｓｓｅｄｔｈｅＣａｕｃｈｙｐｒｏｂｌｅｍｓｆｏｒｅｑｕａｔｉｏｎ( 1 )ａｎｄｕｔ=(…     

Classical and Quantum Perturbation Theory for Two Non-Resonant Oscillators with Quartic Interaction

We study the classical and quantum perturbation theory for two non-resonant oscillators coupled by a nonlinear quartic interaction. In particular, we analyze the question of quantum corrections to the torus quantization of the classical perturbation theory (semiclassical mechanics). We obtain up to the second order of perturbation theory an explicit analytical formula for the quantum energy levels, which is the semiclassical one plus quantum corrections. We compare the exact quantum levels obtained numerically to the semiclassical levels studying also the effects of quantum corrections.Sommario. Si studia la teoria perturbativa classica e quantistica per due oscillatori non risonanti accoppiati tramite una interazione non lineare quartica. In particolare si analizza il problema delle correzioni quantistiche alla quantizzazione dei tori della teoria perturbativa classica (meccanica semiclassica). Si ottiene, al secondo ordine della teoria perturbativa, una formula analitica per i livelli energetici, che è quella semiclassica con l'aggiunta di correzioni quantistiche. Si confrontano i livelli energetici esatti ottenuti numericamente con quelli semiclassici, studiando anche gli effetti delle correzioni quantistiche.     

Physicochemical Model of Hypersonic Rarefied Gas Flow past Bodies

The effect of the internal molecular degrees of freedom on the flow field and heat transfer in hypersonic rarefied gas flow past a cylinder or sphere is investigated using the direct statistical simulation (Monte-Carlo) method. The variable-diameter rough spherical molecule model (VRS-model) is generalized to include the case of energy exchange between the translational and vibrational degrees of freedom. The interaction between diatomic molecules with allowance for vibrational degrees of freedom is simulated as the interaction of classical or quantum-mechanical harmonic and anharmonic oscillators in the external force approximation. A model of the dissociation of a diatomic gas is proposed.     

Nonequilibrium dissociation of diatomic molecules in flows with convective and diffusive particle transport

The nonequilibrium effects in the kinetics of the thermal dissociation which occurs in a streaming gas of diatomic molecules are investigated. Expressions are obtained for the macroscopic reaction rate and the vibrational energy distribution of the molecules, taking into account the influence of the gas motion. Cases of flows with convective and diffusive particle transport are considered. The dissociating molecules are simulated by cutoff harmonic oscillators. The vibrational kinetics is described in the framework of the so-called diffusion approximation.Translated fron Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6, pp. 147–153, November–December, 1985.