可激发气体振动弛豫时间的两频点声测量重建算法

振动弛豫时间是可激发气体分子内外自由度能量转移速率的宏观体现,它决定了声吸收谱峰值点对应的弛豫频率.本文给出了等温、绝热定压和绝热定容三种不同热力学过程下振动弛豫时间的相互关系;基于Petculescu和Lueptow[2005 Phys.Rev.Lett.94 238301]的弛豫过程合成算法,推导了单一压强下两频点声测量值的弛豫时间重建算法.该算法可应用于等温、绝热定压、绝热定容弛豫时间和弛豫频率的重建测量,并避免了弛豫时间传统声测量方法需要不断改变气体腔体压强的问题.仿真结果表明,对于室温下CO_2,CH_4,Cl_2,N_2和O_2组成的多种气体,重建的弛豫时间和弛豫频率与实验数据相符.     

基于声弛豫频率的可激发气体压强合成算法

声弛豫频率是声吸收谱峰值点的频率,包含可激发气体成分、环境温度和压强信息.利用声弛豫频率线性正比气体压强的特性,提出一种通过两频点声吸收系数和声速测量值计算声弛豫频率,并通过查表方式合成气体压强的算法.算法的声弛豫频率测量误差具有随声测量值误差线性变换的特性,且当两频点的声吸收测量误差相等时,压强的合成误差为零.对于一定温度下的甲烷及其混合气体,仿真计算证明算法的有效性和声测量误差的稳健性.提供一种简单、稳健性好、可实时连续在线检测可激发气体腔体压强的声学方法.     

关於流体的容变粘滞弹性理论及其在声吸收现象中的应用

在这篇论文里我们证明,与某些作者所了解的不同,我们的流体的容变粘滞弹性理论不仅仅是在结构弛豫的情况中有效,而是对所有三种弛豫——热弛豫、结构弛豫与化学弛豫——都是同样有效的。从我们的容变不可逆性方程可以推到Herzfeld与Rice原为热弛豫所假定的热不可逆性方程。又可以证明的是在化学弛豫的情况中我们的容变不可逆性方程也包含着Liebermann由分子运动理论考究所得到的化学不可逆性方程。关于这理论在声吸收及速变现象中的应用,我们证明利用适当的热力学考究便可以从我们的压缩性理论所给的结果直接推到在热弛豫情况下有效的Bourgin-Kneser方程及在化学弛豫情况下可以有效的Liebermann方程。这个推导并揭发出来Liebermann的声吸收方程仅对液体说可以是一个良好的近似。我们附带地指出,在气体的情况中,某些已发表的声吸收及速变的实量结果的准确度已可以使我们从这些结果来算定气体的静态与立刻两压缩系数β₀及β_∞,从而确定热容量的两比值γ₀及γ_∞与外态内态两热容量C^(e)及C⁽ⁱ⁾。这样我们又能从这些结果取得一些有关分子构造及分子碰撞过程中能量转移的结论。最后,我们讨论了我们的容变粘滞系数的定义的适当性。     

基于声吸收谱峰值点的天然气燃烧特性检测理论

天然气的成分构成会随产地来源变化而不同, 使其具有不同的燃烧特性和经济价值.本文利用声吸收谱峰值点随气体成分变化而改变的声分子弛豫现象, 提出一种天然气燃烧特性检测理论.它基于两频点上声测量值可合成声吸收谱峰值点, 且依赖于频率的声吸收谱可由峰值点重建的物理原理; 可利用峰值点对应的特征量——弛豫频率和弛豫吸收最大值与气体成分的关系, 从两个维度同时定量检测天然气成分.该理论避免了传统上测量声吸收谱峰值点方法需要不断改变气体腔体压强的问题, 还具有无需测量气体密度的优点.     

混合气体声复合弛豫频谱的解析模型

为研究声传播和分子多模式振动能量弛豫的相互关系,本文提出了一种混合气体声 复合弛豫频谱的解析模型.该模型从振动模式微观能量转移及其耦合形成宏观弛豫过程两个角度, 分析了依赖于声频率的混合气体有效热容.并通过求解振动模式能量转移的通用弛豫方程, 最终得到可同时体现主副弛豫过程的声弛豫吸收和声频散的解析结果.仿真结果表明, 对于CO₂, CH₄, N₂和O₂组成的多种混合气体, 该模型的声吸收谱与实验数据相符,峰值误差在1%以内,且反映了多振动模式形成的 声复合弛豫吸收谱上通常仅会显现1-2个吸收波峰的物理现象.与已有模型相比, 本解析模型可直接求出混合气体声弛豫频谱上特征点的解析形式,并利于对其进行定性定量分析. 从而为研究声传播特性与气体分子弛豫特性的相互关系提供了一个有效理论模型.     

声弛豫过程影响下的气体平衡态热容合成方法及其在气体检测中的应用

声扰动形成的分子振动弛豫过程使得气体热容成为依赖于声频率的有效热容,导致随频率变化的声速频散和声弛豫吸收。本文基于单弛豫过程合成算法,提出一种基于两频点声速和声吸收测量值的气体平衡态热容合成方法。该方法两个测量声频点只需在声弛豫吸收显著的频率范围即可分别合成可激发气体分子内外自由度热容,并有效消除声弛豫过程对气体平衡态热容测量结果的影响。对于室温下由CO₂、CH₄、Cl₂、N₂和O₂组成的多种气体,合成的气体热容值与基于Planck-Einstein公式的热力学理论计算结果相符,相比实验数据最大相对误差为3.51%。合成的转动和振动热容还可应用于气体分子几何结构、振动频率大小和混合气体摩尔分数的检测。      

可激发气体分子声弛豫过程振动模式能量转移速率计算

研究可激发气体中振动模式能量转移速率和声弛豫过程形成的关系,将单一气体Tanczos弛豫方程理论[J.Chem.Phys.25,439(1956)]扩展应用于混合气体中振动模式的振动-振动(V-V)和振动-平动(V-T)能量转移速率的计算。在室温下CO₂,CH₄,CL₂,N₂和O₂组成的多种混合气体中,振动模式能量转移速率的计算结果表明:对于多个振动模式所形成的声复合弛豫过程,各振动模式的声激发能可由V-V能量转移相互耦合后传递给具有最快V-T转移速率的最低振动频率振动模式,再通过该振动模式的V-T转移退激发形成主弛豫过程。这种选择最快转移路径的声激发量弛豫方式,造成了大多数可激发气体中声弛豫吸收谱的实测数据只存在一个吸收峰的现象。从而提供了一个可通过计算微观振动能量转移速率分析混合气体声弛豫过程形成机理的理论模型。      

Calculation of vibrational energy transition rates in acoustic relaxation processes for excitable gas molecules

To research the correlation between vibrational energy transition rates and acoustic relaxation processes in excitable gases, the vibrational relaxation theory provided by Tanczos [J.Chem. Phys. 25, 439(1956)] is applied to calculate the energy transition rates of VibrationalVibrational(V-V) and Vibrational-Translational(V-T) energy transfer in gas mixtures. The results of calculation for the multi-relaxation processes in various gas mixtures, consisting of carbon dioxide, methane, chlorine, nitrogen, and oxygen at room temperature, demonstrate that the acoustic energy stagnated in every vibrational mode is coupled with each other through V-V energy exchanges. The vibrational excitation energy will relax through the V-T de-excitation path of the lowest mode because of its fastest V-T transition rate, resulting in that only one absorption peak can be measured for most of excitable gas mixtures. Thus, an effective model is provided to analyze how the vibrational energy transition rates affect the characteristics of acoustic relaxation processes and acoustic propagation in excitable gas mixtures.     

Decoupling multimode vibrational relaxations in multi-component gas mixtures: Analysis of sound relaxational absorption spectra

Decoupling the complicated vibrational-vibrational (V-V) coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our previous work [Acta Phys. Sin. 61 174301 (2012)], an analytical model to predict the sound absorption from vibrational relaxation in a gas medium is proposed. In this paper, we develop the model to decouple the V-V coupled energy to each vibrational- translational deexcitation path, and analyze how the multimode relaxations form the peaks of sound absorption spectra in gas mixtures. We prove that a multimode relaxation is the sum of its decoupled single-relaxation processes, and only the decoupled process with a significant isochoric-molar-heat can be observed as an absorption peak. The decoupling model clarifies the essential processes behind the peaks in spectra arising from the multimode relaxations in multi-component gas mixtures. The simulation validates the proposed decoupling model.     

Synthesizing primary molecular relaxation processes in excitable gases using a two-frequency reconstructive algorithm

Identifying molecular relaxation processes in excitable gases remains challenging. An algorithm that reconstructs the primary relaxation processes is presented. Based on measurements of acoustic attenuation and sound speed at two frequencies, it synthesizes the entire frequency dependence of the complex effective specific heat of the gas, which is the macroscopic "footprint" of relaxation effects. The algorithm is based on the fact that for a simple relaxation process, such as occurs in many polyatomic gases at temperatures around 300 K, the effective specific heat traces a semicircle in the complex plane as a function of frequency. Knowing the high-frequency or instantaneous value of the specific heat provides the capability to not only sense the presence, but also infer the nature and, for mixtures of unlike-symmetry molecules, the concentration of foreign molecules leaking in a host gas.     

玻璃超声吸收的红外发散理论

本文采用低频涨落、耗散、弛豫过程的统一理论来研究玻璃热活化弛豫过程的超声吸收。与现有的弛豫时间分布理论不同,只采用单一弛豫时间τ_p,但可以说明弛豫时间分布理论所不能解决的玻璃超声吸收的实验特征,并解释这些实验特征与具体材料无关的普适性。 关键词：     

Sound propagation in saturated gas–vapor–droplet suspensions considering the effect of transpiration on droplet evaporation

The sound attenuation and dispersion in saturated gas–vapor–droplet mixtures with evaporation has been investigated theoretically. The theory is based on an extension of the work of Davidson (1975) to accommodate the effects of transpiration on the linear particle relaxation processes of mass, momentum and energy transfer. It is shown that the inclusion of transpiration in the presence of mass transfer improves the agreement between the theory and the experimental data of Cole and Dobbins (1971) for sound attenuation in air–water fogs at low droplet mass concentrations. The results suggest that transpiration has an appreciable effect on both sound absorption and dispersion for both low and high droplet mass concentrations.     

Relaxation of Translational Energy in Binary Mixtures of Dilute Gases Composed of Hard Spheres

Analytical expressions for the relaxation time τ necessary for the equilibration of translational energies of components in binary mixtures of dilute gases composed of hard spheres are derived. An expression for the collision number Z describing the mean number of collisions of one particle during the relaxation time is also given. The derivation has been performed for the very beginning of the relaxation and we choose the initial translational energy of the sort which is in excess to be equal to zero. Computer results obtained by a direct simulation method of solution of the Boltzmann equation do not only confirm these results but also show them to be valid for a relatively long part of the equilibration.     

Dielectric and anelastic relaxation of crystals containing point defects. II

In part I (1965, Adv. Phys., 14, 101), a theory was developed which treated the thermodynamics of dielectric and anelastic relaxation due to point defects in crystals from the viewpoint of the point symmetry of the defect as well as of the crystal. In the present paper this theory is extended to treat the kinetics of relaxation. Equations are derived which express the relaxation times of electrically and stress active modes of relaxation in terms of the rates of reorientation between one particular defect orientation and all of the other equivalent configurations. Explicit expressions are then given for these relaxation times for commonly occurring crystal and defect symmetries. The reorientation frequencies which appear in these expressions may be converted into the appropriate atom or ion jump rates; this final step can generally be carried out merely by inspection of the crystal model. The possibility that two or more relaxations due to a given point defect may be widely separated on a frequency or temperature scale (a situation which is called a ‘frozen-free split’), and the anomalies connected with such behaviour, are discussed. Finally, various examples which have been studied in the literature, of relaxations due to point defects, are reviewed in the framework of the present theory.     

Calculating vibrational mode contributions to sound absorption in excitable gas mixtures by decomposing multi-relaxation absorption spectroscopy

Sound relaxational absorption spectroscopy of excitable gas mixtures is potentially applied for gas composition detection. The relaxation of vibrational modes of gas molecules determines the sound relaxational absorption. However, to our knowledge, the contribution of each vibrational mode available in gas mixtures to sound multi-relaxation absorption has not been calculated in existing literature. In this paper, based on the decoupled expression of the effective isochoric molar heat for a gas mixture, a sound multi-relaxation absorption spectrum is decomposed into the sum of single-relaxation spectra. From this decomposable characteristic, the contribution of each vibrational mode available in the gaseous medium to the multi-relaxation absorption is obtained at room temperature. For various gas compositions including carbon dioxide, methane, nitrogen etc., the calculated contributions of vibrational modes are verified by the comparison with experiment data. We prove the following views with quantifiable outcomes that the primary molecular relaxation process associated with the lowest mode plays the major role in acoustic relaxational absorption of gas mixtures; the mode with lower vibrational frequency provides higher contribution to the primary relaxation process. This work could provide a deeper insight into the relationship between the sound relaxational absorption spectroscopy and gas molecules.     

The Electron Relaxation to Stationary States in Collision Dominated Plasmas in Molecular Gases

The temporal collision dominated relaxation of electrons to new stationary states, starting from initial stationary states and due to jump-like changes of the electric field, was studied in the plasmas of the molecular gases N₂ and CO. Numerical solving of the time dependent Boltzmann equation for the electrons yields the temporal evolution of their energy distribution function and of resulting macroscopic quantities. The varying relaxation due to different values of the field strength in the final stationary state has been investigated considering the molecules of the plasma only as vibrationally non-excited and, in another case, including the additional impact of collisions with vibrationally excited molecules. The results obtained are discussed and, in particular, the relaxation times found for the transitions to the new stationary states are analysed on the basis of the energy transfer effectiveness by the collision processes. An approximative microphysical basis for the understanding of the main features of the relaxation in such complex molecular gas plasmas could be obtained.     

Excitation dynamics during the multiphoton absorption in SF6+buffer-gas mixtures

A detailed analysis of the total average number of absorbed photons 〈n〉_total during Infrared multiphoton absorption processes in mixtures of SF₆-Ar, N₂ and CH₄ buffer gases is presented. The results for 〈n〉_total are deduced using pulsed photoacoustic technique in collisional regime. Complete analysis is based on the theoretical generalized coupled two-level model (GCT) and its application to different gas mixtures. Evaluation of partial 〈n〉_coll. values is presented too, obtained using the results from time-resolved optoacoustic (TROA) and time-resolved absorption (TRA) methods for V-T relaxation times (τ_V-T) and the saturable absorber (SA) method for R,R-T relaxation times (τ_rot.-rel.), and applying them directly to the GCT model. All methods (TROA and SA) and the GCT model use the same photoacoustic results from our experiment under identical experimental conditions.     

Ultrasonic absorption frequency dependence of two widely used anti-cancer drugs: doxorubicin and daunorubicin

Low intensity ultrasound (approximately 10⁻⁶ W cm⁻²) in the frequency range 0.5–6.0 MHz was employed to investigate the ultrasound absorption properties of doxorubicin (DOX) at several temperatures. At physiological temperatures, we found enhanced ultrasound absorption from DOX, and its closely related analogue daunorubicin (DNR), in the upper kilohertz frequency range. The findings do not conform to classical theory of ultrasound absorption, thus suggesting an ultrasound coupling with the drug molecules via structural and/or chemical relaxation processes. The absorption spectra are analysed from the point of view of the non-classical theory of sound absorption due to physical and/or chemical relaxations. Only one spectral difference between the two anti-cancer agents is observed, around 2 MHz, and may be attributed to the sole difference in the chemical make-up of the side chain of the two antibiotics.     

多原子分子气体中声波弛豫衰减谱的重建算法

提出了一种宽频率范围的弛豫衰减谱重建算法,并采用基于SSH理论的方法和基于实验数据的方法估计气体的有效弛豫时间.通过该算法得到了包括氮气、甲烷、氧气、二氧化碳和水蒸气在内的多种多原子分子混合气体的声衰减谱,研究的声波频率范围从1Hz到10GHz.与预测弛豫衰减的DL模型的结果比较表明,该算法获得的弛豫衰减谱结果与之相符,其预测精度取决于对分子弛豫过程的正确认识.另外该算法还被用于几种混合气体中水蒸气和二氧化碳含量的分析,其结果表明弛豫衰减谱可被用于定量分析多原子分子气体的成分组成,这使得实现高灵敏度地检测气体成分的智能声气体传感技术成为可能. 关键词： 声弛豫衰减 有效弛豫时间 重建算法 声气体传感器     

Coherent transients in gases

A great variety of coherent transient processes in atomic and molecular gases is investigated. The degeneracy with respect to magnetic sublevels, which is typical of working levels of atomic and molecular transitions in gases, leads to new phenomena. In particular, the non-Faraday rotation of the coherent-response polarization vector at the 0 ↔ 1 transition is investigated in the presence of the longitudinal magnetic field in the ¹⁷⁴Yb vapor for both photon echo and stimulated photon echo. A specific relaxation channel that involves the depolarizing collisions emerges in a gas due to the degeneracy of working levels. Such collisions are especially important for atoms and are also observed in molecules. The anisotropy of the depolarizing collisions leads to a new phenomenon of the collision photon echo, which is experimentally demonstrated for the 0 ↔ 1 transition in the ¹⁷⁴Yb mixtures with atomic buffers. The velocity-dependent relaxation rates are observed for various coherent phenomena in molecular gases. The coherent control of a few coherent transient processes is implemented.