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.     

高温非平衡流动中的氧分子振动态精细分析

高超声速流动在头激波压缩后常处于高 温条件下的热化学非平衡状态. 本文采用态-态方法和双温度模型计算分析了一维正激波后和高超声速钝体绕流驻点线上的氧气热化学非平衡流动. 态-态方法将氧气的每个振动能级当成独立的组分,通过耦合 Euler 方程或驻点线上的降维 Navier-Stokes 方程,数值求解得 到了高温流动中的精细热化学非平衡状态. 而双温度模型假设氧气的振动能级服从 Boltzmann 分布,通过求解振动能方程得到振动温度. 一维正激波后热化学松弛过程的计算结果表明,态-态计算预测的温度分布和氧原子浓度分布较好地吻合了文 献中的实验结果,而经典的双温度模型的预测结果误差较大,且不同双温度模型的计算结果比较发散. 态-态方法详细地给出了所有振动能级的变化过程. 无论是正激波还是脱体激波后的流场,都是高振动能级首先得到激发;但是数密度大的低振动能级先达到热平衡,而高能级 分子要经过很长距离后才能达到热平衡. 在驻点附近,复合反应生成的氧气分子处于高振动能级,导致高振动能级分子数密度显著高于平衡分布. 计算还发现,经典双温度模型的离解反应速率明显偏离态-态计算结果,无法准确体现振动离解耦合效应对离解反应 速率的影响,但是 Park 双温度模型将离解失去的振动能取为 0.3$\sim 高超声速流动在头激波压缩后常处于高 温条件下的热化学非平衡状态. 本文采用态-态方法和双温度模型计算分析了一维正激波后和高超声速钝体绕流驻点线上的氧气热化学非平衡流动. 态-态方法将氧气的每个振动能级当成独立的组分,通过耦合 Euler 方程或驻点线上的降维 Navier-Stokes 方程,数值求解得 到了高温流动中的精细热化学非平衡状态. 而双温度模型假设氧气的振动能级服从 Boltzmann 分布,通过求解振动能方程得到振动温度. 一维正激波后热化学松弛过程的计算结果表明,态-态计算预测的温度分布和氧原子浓度分布较好地吻合了文 献中的实验结果,而经典的双温度模型的预测结果误差较大,且不同双温度模型的计算结果比较发散. 态-态方法详细地给出了所有振动能级的变化过程. 无论是正激波还是脱体激波后的流场,都是高振动能级首先得到激发;但是数密度大的低振动能级先达到热平衡,而高能级 分子要经过很长距离后才能达到热平衡. 在驻点附近,复合反应生成的氧气分子处于高振动能级,导致高振动能级分子数密度显著高于平衡分布. 计算还发现,经典双温度模型的离解反应速率明显偏离态-态计算结果,无法准确体现振动离解耦合效应对离解反应 速率的影响,但是 Park 双温度模型将离解失去的振动能取为 0.3$\sim $0.5 倍分子离解能是比较合理的.     

Calculation of nonequilibrium distribution functions and dissociation rate of diatomic molecules in a boundary layer

The effect of the nonequilibrium velocity and rotation distributions of the dissociating molecules on the population of the upper vibrational levels and the dissociation rate, when the reaction kinetics are strongly influenced by the motion of the gas, is analyzed by solving the Boltzmann equation by a method permitting the calculation of the distribution function under conditions of strong disequilibrium.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 2, pp. 165–172, March–April, 1989.     

Quasiequilibrium model of the kinetics of coupled modes of CO2 molecules

The correct allowance for the influence of anharmonicity in the vibrational spectrum of CO₂ on the level distribution of molecules under nonequilibrium conditions, when the vibrational temperature departs significantly from the gas temperature, has become especially urgent in connection with obtaining generation on a number of long-wavelength transitions of CO₂ molecules [1, 2]. The shifts in the levels of coupled modes (symmetric and deformation) are due mainly to Fermi resonance and can reach a considerable value, comparable with the gas temperature even for low levels. In [3] the main features of the quasisteady level distribution of coupled modes were clarified within the framework of the Treanor model of vibrational kinetics. The influence of the ascending flux of quanta, excited by VV exchange under nonequilibrium conditions, on the vibrational distribution was considered in [4–6]. In the present paper we propose a quasiequilibrium model of CO₂ kinetics, obtained without presuming quasisteadiness of the ascending flux of quanta, and making it possible, in contrast to [3–6] to describe the dynamics of the variation of the distribution of molecules among multiplets as a result of processes of VV exchange and VT relaxation between multiplets, with allowance for possible processes of pumping by outside sources. With a Boltzmann population distribution within the multiplets, having the translational temperature of the gas, the problem of studying relaxation in coupled modes is reduced to the equations for an effective anharmonic oscillator with levels corresponding to the multiplets of CO₂ molecules. In this case the levels of the effective oscillator are degenerate with a multiplicity equal to the number of levels in the corresponding multiplet, and they have an anharmonicity constant dependent on the gas temperature. The population distribution of the effective oscillator can be studied by methods developed for the investigation cf a one-mode anharmonic oscillator. The proposed quasiequilibrium model was used for a numerical calculations of the temporal evolution of the distribution function of CO₂ molecules over the levels of coupled modes under the conditions of an extremely maintained discharge.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 3, pp. 16–22, May–June, 1986.     

Effect of Transitional Nonequilibrium on the Molecular–Dissociation Rate in a Hypersonic Shock Wave

The problem of the influence of a nonequilibrium (non–Maxwellian( distribution of translational energy over the degrees of freedom of molecules on the rate of their dissociation in a hypersonic shock wave is considered. An approximate beam—continuous medium model, which was previously applied to describe a hypersonic flow of a perfect gas, was used to study translational nonequilibrium. The degree of dissociation of diatomic molecules inside the shock–wave front, which is caused by the nonequilibrium distribution over the translational degrees of freedom, is evaluated. It is shown that the efficiency of the first inelastic collisions is determined by the dissociation rate exponentially depending on the difference in the kinetic energy of beam molecules and dissociation barrier.     

Thermal dissociation of diatomic molecules in a nonisothermal two-temperature boundary layer

Nonequilibrium thermal dissociation in a nonisothermal boundary layer in a mixture of Morse anharmonic oscillators — molecules of a diatomic gas and its atoms — is considered within the framework of the ladder mechanism. The local nonlinear nonequilibrium corrections to the two-temperature macroscopic dissociation rate, which depend, in particular, on the translational and vibrational temperature gradients and the degree of dissociation, are determined.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, pp. 191–201, March–April, 1996.     

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.     

Model of the physico-chemical kinetics behind the front of a very intense shock wave in air

A model of the physico-chemical kinetics of the reactions taking place behind the front of an intense shock wave propagating in air with a speed of 9–14 km/s is proposed. The problem of describing the chemical reactions, namely, molecular dissociation and exchange reactions involving vibrationally excited molecules in the absence of vibrational equilibrium, is solved. The vital role of the vibrational excitation delay in the dissociation of oxygen and nitrogen is established. The rate of the exchange reaction between nitrogen molecules and oxygen atoms in the shock wave depends only slightly on the vibrational excitation level. It is demonstrated that the rate constants for thermally nonequilibrium dissociation reactions can be represented within the framework of the one-temperature approximation at constant vibrational temperatures of the dissociating species satisfying quasi-stationary conditions.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, pp. 169–182, March–April, 1995.     

Rotation-vibration-dissociation interaction in a multicomponent nonequilibrium viscous shock layer

A new, simple and physically adequate method of calculating vibrationally nonequilibrium dissociation constants is proposed on the basis of a dissociation model which takes into account the equilibrium excitation of the rotational degrees of freedom of the molecules and the nonequilibrium excitation of vibrational quantum states. This rotation-vibration-dissociation interaction model contains only the indeterminacy associated with the indeterminacy of the experimental data on the interaction potentials and the collision cross sections of the components. In the case of thermodynamic equilibrium the model gives values of the dissociation constants close to those generally accepted. The use of this model in multicomponent nonequilibrium total viscous shock layer calculations gives values for the shock detachment distance within 5% of the experimental values. The indeterminacy in the values of the vibrational energy lost by air molecules during dissociation and recovered during recombination does not lead to serious errors in the macrocharacteristics of the flow. The nonequilibrium excitation of vibrational degrees of freedom proves to be not so important in computing the macrocharacteristics of the flow as previously assumed and the existing algorithms for calculating chemically nonequilibrium flows on the assumption of thermodynamic equilibrium can be used with satisfactory accuracy for calculating the values of the heat flux, the position of the shock wave, and the temperature and pressure in the shock layer for partially dissociated and ionized air.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 6, pp. 166–180, November–December, 1994.     

Influence of the initial spatially inhomogeneous temperature perturbations on vibrational relaxation dynamics

The vibrational relaxation of a nonequilibrium molecular gas (T_V>T) plays an important role in the physics of gas lasers, laser chemistry [1], and plasma chemistry [2]. This paper is devoted to an analysis of the dynamics of V-T relaxation with spatially inhomogeneous perturbations of the translational temperature taken into account.Translated from Zhurnal Prikladnoi Mekhaniki i Technicheskoi Fiziki, No. 6, pp. 77–80, November–December, 1984.     

Three-dimensional computer model of nonequilibrium aerophysics of the spacecraft entering in the Martian atmosphere

A three-dimensional computer model of nonequilibrium aerophysics of the spacecraft entering in the Martian atmosphere and landing on the planet surface is presented. The model is based on the system of Navier-Stokes equations, the energy conservation equation in the form of the Fourier-Kirchhoff equation for the translational temperature, the system of equations of vibrational kinetics for six vibrational modes of N₂, O₂, CO₂ and CO molecules, and the equation of selective thermal radiation transfer in the multigroup spectral approximation. The results of two-dimensional and threedimensional calculations of the nonequilibrium flowfield and the convective and radiative heating of the EXOMARS spacecraft surface are presented. The calculations are performed on regular multiblock curvilinear grids using the NERAT-2D and NERAT-3D computer codes developed in the Institute for Problems in Mechanics of the Russian Academy of Sciences.     

Influence of Vibrational Relaxation on the Pulsation Activity in Flows of an Excited Diatomic Gas

The influence of vibrational relaxation on the nonlinear evolution of a large vortex structure in a shear flow of a highly nonequilibrium diatomic gas is studied. Calculations are performed using the equations of twotemperature gas dynamics for a viscous heatconducting gas. Relaxation of the temperature of vibrational levels of gas molecules to equilibrium is described by the Landau–Teller equation. The contribution of the relaxation of rotational levels is taken into account by the bulk viscosity in the stress tensor. It is shown that in the presence of only the relaxation process with no viscous dissipation, the damping of the kinetic energy of perturbations and Reynolds stresses increases by up to 10 % compared to the case of thermal equilibrium. For high (actually attainable) degrees of excitation of the vibrational mode, moderate dynamic and bulk viscosities, and a typical relaxation time comparable to flow time, the relative effect of perturbation damping reaches 15%.     

The flow of a gas consisting of asymmetric dipole molecules in a field of resonance radiation

The special properties of the flow of a molecular gas in a field of continuous radiation the frequency of which is resonant to the frequency of the intermodal vibrational-rotational transition has been considered previously in [1]. However, this did not take account of a possibility of an energy flux arising from translational degrees of freedom of the gas molecules into vibrational degrees of freedom as a result of the rotational-translational (R-T) transfer. This effect was discussed in [2] for the absorption by a gas consisting of diatomic molecules of radiation momentum in the P-branch of a vibrational-rotational transition. As will be shown below, for asymmetric dipole molecules of the type similar to a symmetric and an asymmetric top, this mechanism of the resonance radiation effect may take place not only under absorption of the radiation in the P-branch, but also in the Q-, and even in the R-branch. The investigation of these effects in the flow of a gas consisting of asymmetric dipole molecules in a resonance radiation field forms the subject of the present study.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 1, pp. 123–137, January–February, 1985.In conclusion we may note that the effects considered can have an important effect on the propagation both of continuous, and of intermittent electromagnetic radiation.     

考虑振动非平衡的可压缩库埃特流动及其传热

新型近空间高超声速飞行器大多具有尖头薄翼的外形,驻点下游机身附近的强剪切流动及气动加热具有显著的非平衡特征.由于加热总量预估和实验测热数据辨识的需要,工程上越来越关注强剪切非平衡流动及气动加热预测问题.本文结合理论建模和直接模拟蒙特卡洛数值模拟,研究了振动非平衡条件下的可压缩库埃特流动的气动力/热问题.首先基于参考温度...     

Nonequilibrium vibration-dissociation phenomena behind a propagating shock wave: Vibrational population calculation

An analysis of nonequilibrium phenomena behind a plane shock is presented concerning the vibrational relaxation and the dissociation of a pure diatomic gas. In the first part, the temperature range is 600 K–2500 K and the dissociation processes are neglected. The population of each vibrational level is computed by solving relaxation and conservation equations. The relaxation process is described by the master equations of each vibrational level. The vibrational transition probabilities appearing in the relaxation equations are calculated analytically and take into account the anharmonicity of molecular vibration and the potential angular dependence. The populations obtained are compared to those calculated using a Treanor model and to those calculated with a nonequilibrium Boltzmann distribution. For moderately high levels significant differences may be observed. The importance of the V-V process is found to be weak for the transitions involving the lowest levels. In the second part, the temperature range is 2500 K–5500K and the dissociation process is taken into account as well as the gas dynamic behavior which did not appear in several recent works. The kinetic equations are transformed to obtain a first order differential system and the resolution of such a system coupled with the conservation equations leads to the population of each vibrational level. The vibrational transition probabilities associated with the atom-molecule interaction are deduced from the cross section calculation used in the first part. The bound-free transition probabilities are obtained, following Marrone and Treanor, assuming that dissociation must occur preferentially from the higher vibrational states: the Marrone and Treanor probability model is extended and employed with an anharmonic oscillator. In the present investigation, behind the shock wave, the evolution of the population distribution expressed as a function of the distance is not monotonous: a lag time appears as shown experimentally in previous works for the macroscopic parameters. For moderately high levels the influence of the anharmonicity and those of the V-V processes appear significant and strongly related. In a general way, in both temperature ranges investigated, the V-V processes reduce the effects of the T-V transfer. Finally the influence of thecharacteristic probability temperature U of Marrone and Treanor is analyzed and a method of determination of local varying U is proposed.     

Gas-dynamic equations involving vibrational relaxation

We derive the gas-dynamic equations in the Navier-Stokes approximation for weak excitation of molecular vibrational states. We determine the distribution function for the density of the numbers determining occupancy of the vibrational states of the molecules. We show that the relaxational pressure is proportional to the deviation of the vibrational energy density from its local-equilibrium value for the temperature of the translational and rotational degrees of freedom of the molecules.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 4, pp. 8–17, July–August, 1972.In conclusion, the author thanks V. N. Zhigulev and V. S. Galkin for a discussion of his results.     

高温气体热化学反应的DSMC微观模型分析

热化学耦合的非平衡现象一直是高温气体热化学问题研究的难点, 制约了诸如爆轰波胞格结构、低温点火速率等现象的分析. 本文以高温氮气离解和氢氧燃烧中的链式置换反应为例, 从微观反应概率、振动态指定的反应速率、热力学非平衡态的宏观反应速率、碰撞后的能量再分配等角度, 分析了直接蒙特卡罗模拟中的典型化学反应模型(TCE, VFD, QK模型)的微观动力学性质. 研究发现, 无论是高活化能的高温离解反应还是低活化能的链式置换反应, 实际参与反应的分子的振动能概率分布都偏离了平衡态的Boltzmann分布, 包含较强振动能额外影响的VFD模型可以很好地模拟高温离解反应, 而TCE (VFD的一个特例)和QK模型对活化能较低的链式置换反应的预测效果相对更好. 此外, 化学反应碰撞后的能量再分配应遵循微观细致平衡原理, 细微的偏差都可能造成平动能和振动能难以达到最终的平衡状态. 直接蒙特卡罗模拟的应用评估结果表明, 化学反应的振动倾向对热化学耦合过程产生了明显的影响, 特别是由于高振动能分子更多地参与了化学反应, 气体平均振动能的下降将影响后续化学反应的进行.      

Influence of nonequilibrium radiation on rarefied gas flow around blunt bodies

The hypersonic nonequilibrium rarefied gas flow is investigated in the neighborhood of the stagnation streamline ahead of a blunt body by taking into account nonequilibrium radiation due to electron excitation for air and carbon dioxide. The analysis is on the basis of a numerical solution of the Navier—Stokes equations simplified under the assumption of local self-similarity of the flow with the Shockwave structure taken into account. It is shown that at low densities, when the shock wave and shock layer thicknesses are of the same order of magnitudes, the two-layer Cheng model becomes inapplicable in the presence of radiation. In this case, the governing process is diffusion of the electronically excited molecules from the shock layer into the forward part of the shock front. The mechanism of the formation of a second luminous plateau on the diagram of the nonequilibrium radiation intensity density is discussed. The combined influence of the limit in collisions and the diffusion transport processes on the intensity of molecular band radiation is considered.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6, pp. 81–87, November–December, 1974.The author is grateful to V. V. Lunev for discussion and remarks during performance of the research.