多元可激发气体声弛豫频率的环境影响分析

推导多元可激发气体中声弛豫频率和环境温度、压强的解析关系.理论分析和仿真计算表明：声弛豫频率线性反比于主弛豫过程的弛豫时间,正比于主弛豫过程的振动耦合热容,反比于外自由度热容;温度升高导致振动耦合热容增加、内外自由度能量转移速率增大引起弛豫时间减少,进而造成声弛豫频率正比于环境温度;压强增加使得分子碰撞速率增加引起弛豫时间减少,进而使得声弛豫频率线性正比于环境压强.     

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.     

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.     

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.     

NO2分子内能传递和弛豫过程的光声和荧光光谱探测

将荧光光谱和光声光谱两种互补的探测技术结合起来,从辐射和无辐射跃迁两个方面,分析了 532nm激光作用下,NO2分子的激发和弛豫过程.发现NO2分子在激光作用下,将跃迁至第一激发电子态.当样品气压较低时,受激NO2分子除辐射荧光外,可通过快速的内能转移过程实现在几个振转能级的再布居;随样品气压的升高,分子间碰撞加剧,受激NO2分子通过分子间的碰撞,实现在多个振转能级的再布居.激光布居能级的荧光辐射效率随样品气压的升高逐渐降低,而长波区域的荧光辐射及光声信号强度逐渐增强,说明在高样品气压条件下,受激NO2分子的弛豫过程除辐射荧光外,还存在很强的碰撞弛豫过程,在碰撞弛豫过程中受激NO2分子将振动能转化为热运动的平动能,引起温度升高而产生很强的声信号.     

高压气体振动弛豫过程的微观研究

此文利用分子动力学计算机模拟方法，研究温度达到一千度，压力为几十万大气压下气体的振动弛豫速率与双原子分子的非谐性及温度的关系，发现振动弛豫速率随双原子分子的非谐性增大而迅速加快，却与温度几乎无关。     

相干喇曼诱导甲烷V-T弛豫过程

本文首次报道了用相干喇曼激光诱导红外荧光的方法,研究多原子分于-OH_4的振动能转移过程,并测出v_4振动能级到平动能转移速率常数为:K_(VL)=(8±)×10_(-5).     

近红外波段CO2分子弛豫动力学效应对光声信号的影响

介绍了一种基于低功率的分布反馈式(DFB)半导体激光器和自行设计的一阶纵向共振光声池构成的共振光声光谱测量系统.该系统具有结构简单、操作方便、价格低廉等优点.通过对光声池的性能进行的研究,实验研究和理论分析具有很好的一致性;系统地研究了近红外1.573μm附近分子弛豫效应对光声探测CO2信号的影响,并给出了相应的理论分析,表明利用分子弛豫效应可有效地提高系统探测灵敏度.     

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.     

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.     

A relaxation times coupling method to construct acoustic relaxation calibration for two-frequency measuring gas compositions

In our previous work (Hu et al., 2014), a method has been proposed to detect gas compositions by locating the acoustic spectral peaks, which can be detected only by two-frequency acoustic measurements in practice. However, as a ‘Detection Calibration’, the effective relaxation area (ERA) constructed by existing theoretical model cannot match the two-frequency measurements when there are more than one strong relaxational components in gas mixtures. This paper proposes a method to construct the ERA by coupling the decoupled single relaxation times together to a whole relaxation time. For gas mixtures with only one single relaxation process, the predicted ERA results match with the experimental data better than those predicted by the existing model. Moreover, for gas mixtures in which more than one relaxation process are significant, the ERA results predicted by the proposed method also match with the detection results of two-frequency measurements better than the existing model. This relaxation time coupling based ERA constructing method is validated by the application in low-quality natural gas detection.     

Kinetic theory of vibrational relaxation in a radiation field: The optic-acoustic effect

A microscopic derivation is presented of the rate equations governing vibrational relaxation occurring in the optic-acoustic effect. Detailed expressions applicable to the spectrophone experiment are given both for an excitation source consisting of a broadband radiation field and for laserdriven systems. It is clear from the present treatment that no real advantage accrues from the use of laser excitation sources in the standard spectrophone experiment, due to the resultant strong dependence of the driving force itself on the mechanical chopper frequency. For broadband radiation field the dependence on the chopper frequency is removed and the standard result containing the Einstein coefficient of induced absorption is recovered. The spectrophone response for the simplest case of a two-level system is given explicitly and its similarity to phenomenologically derived expressions is pointed out.The work of F.R.M. was supported in part by a grant from the National Research Council of Canada. The work of A.T. was supported by the Foundation for Fundamental Research on Matter, which is sponsored by the Netherlands Organization for the Advancement of Pure Research.     

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.     

Submillimeter-wave spectroscopy of HCO in the excited vibrational states

The pure rotational transitions of HCO⁺ in excited vibrational states located below 5000 cm⁻¹ over the ground state have been investigated with a high-sensitivity frequency/magnetic field double modulation submillimeter-wave spectrometer in the frequency range of 280-810 GHz. The ions were generated in an extended negative glow discharge through a gas mixture of a few millitorrs of H₂ and CO and 12 mTorr of Ar buffer gas. Throughout the experiments, the cell was maintained at liquid nitrogen temperature. In the present study, we have determined accurate molecular constants for the excited vibrational states. Our analysis suggests that there may be a higher order Coriolis interaction between the (0 3 1) and (1 2 0) states. In previous investigations, the Stark effect caused by the electric field present in the discharge plasma was cited as a reason for non-observations of low-J lines in the (02²0) and for the systematic shifts observed for low-J lines in the (01¹0), (02²0), (03¹0), and (04²0) states of HCO⁺ as well as DCO⁺. In the present investigation, some low-J lines in the (02²0) and (04²0) states have been observed in emission. Furthermore, J = 8-7, J = 9-8 lines in (03^1e1) were detected in emission. This finding indicates that missing low-J lines for the Δ sublevel obtained in the past is not due to the Stark effect but due to small population differences in those levels.     

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.     

部分气体双原子分子的完全振动能谱和离解能的精确研究

鉴于气体双原子分子H2、O2、N2和CO的高振动激发态能级和离解行为在实际研究中的重要性,本文应用代数方法(AM)和代数能量方法(AEM),以部分气体双原子分子有限的实验能级[Ev]为基础,获得了H2-X1∑ g、O2-A3∑ u、O2-c1∑-u、N2-X1∑ g和CO-X1∑ 共5个电子态的完全振动能谱{Ev}及其分子的离解能,为研究部分离解气体的物理和化学性质提供了重要的高振动激发态能级和可靠的离解能数据.