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.     

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。      

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     

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.     

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.     

气体声弛豫过程中有效比热容与弛豫时间的分解对应关系

声在多原子分子气体中传播所引起的弛豫过程是探索气体特性的重要方面. 本文通过研究气体声弛豫过程中振动自由度与平动自由度(V-T)以及振动自由度之间(V-V)的分子能量转移模型, 给出了有效比热容与弛豫时间的分解对应关系及其通用获得方法. 该分解模型与现有的声弛豫模型相比, 反映了分解后的V-T 和V-V弛豫过程中振动比热容与弛豫时间的对应关系, 并发现了较高能级是引起对应声弛豫过程的决定因素. 将基于该分解模型获得的气体声弛豫衰减谱经碰撞直径微调改进后, 比现有理论更接近实验数据, 其结果证明了该分解对应关系的正确性和合理性.     

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.     

Interpretation of anomalous normal state optical conductivity of La-Sr-CuO cuprates

The observed frequency dependent optical response of hole doped cuprate La_1.85Sr_0.15CuO₄ superconductors, has been theoretically analysed. Starting from an effective two-dimensional (2D) interaction potential for superlattice of hole doped cuprates treated as a layered electron gas, the spectral function is formulated. Calculations of the optical conductivity σ(ω) have been made within the two-component scheme: one is the coherent Drude carriers responsible for superconductivity and the other is incoherent motion of carriers from one site to other leads to a pairing between Drude carriers. The approach accounts for the anomalies reported (frequency dependence of optical conductivity) in the optical measurements for the normal state. Estimating the effective mass from specific heat measurement and ε_∞ from band structure calculations for the low-energy charge density waves, the model has only one free parameter, the relaxation rate. The frequency dependent relaxation rates are expressed in terms of memory functions, and the coherent Drude carriers from the effective interaction potential lead to a sharp peak at zero frequency and a long tail at higher frequencies, i.e. in the infrared (IR) region. However, the hopping of carriers from one site to other (incoherent motion of doped carriers) yields a peak value in the optical conductivity centred at mid-IR (MIR) region. We find that both the Drude and hopping carriers in the superlattice of cuprates will contribute to the optical process of conduction in the CuO₂ planes and shows similar results on optical conductivity in the MIR as well as IR frequency regions as those revealed from experiments.     

Relaxation processes in an alternating-current electric field and energy loss mechanisms in hafnium diselenide cointercalated with copper and silver atoms

Samples based on hafnium diselenide intercalated with atoms of two types, Cu_xAg_yHfSe₂ at (x + y) ≤ 0.2, have been synthesized for the first time. The frequency dependences of the components of the complex impedance have been measured using impedance spectroscopy in the frequency range from 1 Hz to 10 MHz, and the specific features of the relaxation processes occurring in samples of different compositions have been analyzed. It has been shown that the characteristic times of these processes depend not only on the total concentration of intercalated atoms, but also on the ratio between them. As the total concentration of copper and silver increases, the onset of frequency dispersion of the complex admittance shifts to the higher frequency range. The relative contributions from the conduction and relaxation polarization losses also change depending on the total and element concentrations of the intercalated atoms.     

On gas phase transitions in a 2D nanopore

A gas distribution function for a 2D nanopore was derived, making possible calculations of thermodynamic characteristics such as pressure and heat capacity. The dependence of pressure and heat capacity on the least nanopore size was considered suggesting the presence of specific phase transitions in the gas in a certain temperature range. The phase transitions are associated with size quantization which results in “effective” interaction (attraction) between gas molecules.     

Triplet-triplet transfer of electronic energy upon nonequilibrium vibrational excitation of triplet molecules

The specific features of the triplet-triplet (T-T) transfer of electronic excitation energy in a gas phase upon nonequilibrium vibrational excitation of the triplet molecules of a donor were studied for an anthraquinone-diacetyl donor-acceptor pair using the time-resolved slow fluoresence of anthraquinone and sensitized phosphorescence of diacetyl. It is shown that in the gas phase, which allows regular control of the number of collisions, competition between the processes of T-T transfer and intermolecular vibrational relaxation is observed for nanosecond time resolution. The T-T transfer rate for the molecular system investigated exceeded the rate of intermolecular vibrational relaxation k_V in the triplet state T₁ of the donor. The effectiveness of the T-T transfer of energy by vibrationally excited molecules turned out to be higher than the effectiveness of transfer by thermalized ones, but even the highest of them was much less than unity. An increase in the equilibrium temperature of vapors led to a decrease in the effectiveness of transfer for both vibrationally excited and thermalized triplet molecules, thus indicating the importance of the collisional complex in the intermolecular process studied. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 474–479, July–August, 2000.     

基于三频点声速测量的气体压强合成算法

利用声速测量精度高, 测量方法简单的特点, 提出一种基于三个频率点测量声速合成气体压强的算法。首先在三个频率点测量声速, 然后计算得到声速频散谱拐点的弛豫频率, 最后根据弛豫频率与压强成线性正比的关系得到气体压强, 仿真结果验证了该算法的可行性。为在线实时检测气体腔体压强提供了一种技术简单、精度高的超声方法。     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

The equation of state of a microinhomogeneous medium and the frequency dependence of its elastic nonlinearity

In the framework of a rheological model, a nonlinear dynamic equation of state of a microinhomogeneous medium containing nonlinear viscoelastic inclusions is derived. The frequency dependences of the effective nonlinear parameters are determined for the difference frequency and second harmonic generation processes in the case of a quadratic elastic nonlinearity. It is shown that the frequency dependence of the nonlinear elasticity of the medium is governed by the linear relaxation response of the inclusions at the primary excitation frequency, as well as by the relaxation of the inclusions at the nonlinear generation frequencies.     

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.     

Dielectric Relaxations and Structures of Nanoclay in Solution Cast Poly(Ethylene Oxide)– Montmorillonite Clay Nanocomposites

The relative complex dielectric function, electric modulus and alternating current electrical conductivity spectra and complex impedance plane plots of aqueous solution cast poly(ethylene oxide)–montmorillonite clay (PEO–MMT) nanocomposite films were investigated over the frequency range 20 Hz to 1 MHz at ambient temperature. The intercalated and exfoliated structures of nanoclay dispersed in PEO matrix were recognized by the significant change in real part of dielectric function with clay concentration in the range 0%–20 wt%. The relaxation times corresponding to PEO chain segmental motion and ionic conduction relaxation processes were used to explore the interactions compatibility between PEO molecules and the dispersed MMT clay nanoplatelets and their effect on PEO chain dynamics. Real part of conductivity spectra of these nanocomposites over five decades of frequency has nonlinear behavior, which is influenced by the MMT clay concentration. The complex impedance plane plots confirm the bulk properties of these nanocomposites over the experimental frequency range.     

Use of the tikhonov regularization method in automated mathematical analysis of dielectric spectrometry data

Extensive information has now been accumulated on dielectric relaxation processes and their relationships to the structure of complex polar molecules. At the same time, however, the number of experimental methods for rapid determination of the range of relaxation times is fairly small. The purpose of this work is to determine the possibilities for experimental evaluation of the type of distribution function of the dielectric relaxation times and to work out an algorithm for computing it under the conditions of an automated experiment.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 102–108, October, 1991.     

Sound waves in a nonequilibrium molecular gas

We consider relaxation processes of dynamics of a nonequilibrium vibrationally excited gas (T_v>T₀). It is shown that the effective heat capacities can become negative in such a medium. This leads to anomalous effects during propagation of long-wave sound: there exist regions (in the parameter T_v/T₀) of sharp enhancement and reduction of its speed, as well as regions where low-frequency sound can generally not propagate. Instability conditions are investigated for various temperature dependences of vibrational relaxation times. It is shown that in a certain region of T_v/T₀ values one has amplification of sound waves, related to the formation of second viscosity in these media. In this case a change in the amount of medium nonequilibrium can vary the sound frequency corresponding to maximum amplification.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 53–58, July, 1986.