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。      

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.     

常温下氢气声转动弛豫模型研究

氢气声弛豫过程主要由氢气分子的转动弛豫决定.然而,当前大部分声弛豫模型是基于气体分子的振动弛豫,并不适用于氢气.本文利用理想气体焓变与定压热容的关系,提出了一种基于氢气分子转动的弛豫模型,并讨论了转动弛豫和振动弛豫的相似与不同.该模型不仅适用于氢气,还能够和其他气体的振动弛豫模型相结合求解混合气体的声弛豫吸收谱和声速频谱.仿真结果表明,对于H_2,N_2/H_2,CO_2/H_2等气体,该模型生成的声速、声弛豫谱曲线与实验数据符合.本模型为包含氢气的混合气体声学探测提供了一个有效的理论模型.     

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     

磁约束放电CO激光模型

建立了磁约束放电CO激光的模型.在该模型下分析、计算了CO气体放电系统电子的能量分布 函数;CO分子的电子碰撞激发概率以及CO分子的振动-振动(V-V),振动-平动(V-T)激发概率 ;CO分子各振动态的布居数分布和对应的小信号激光增益系数.研究表明,由于磁场的加入C O分子振动态布居数分布出现凹陷.在该区域获得了更大激光的小信号增益. 关键词： CO激光 磁约束 布居数 小信号增益 激发系数     

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。      

重复频率脉冲大气放电中氮气的振动温度

氮气分子的振动自由度在大气放电低温等离子体中会被高度激发。从振动能级的简谐振子模型和Boltzmann分布近似出发,研究重复频率脉冲放电中振动温度的变化行为。结果表明,决定重频条件下振动温度的主要过程是电子碰撞振动激发和振动-平动弛豫,而在振动能级高度激发的情形下其与氧原子的化学反应也会产生影响。对于振动激发过程,通过跃迁反比相似率推导出的特征弛豫时间与动理学模型符合较好。在振动-平动弛豫中占主导贡献的为干燥大气中的氧原子或潮湿大气中的水分子。当氧原子数密度为1014 cm-3时,若初始振动温度在5000 K,在化学反应过程中振动能量的特征弛豫时间在0.1~1 s量级。     

HBr(X~1Σ~+ν~″=5)分子与H_2,N_2,CO_2和HBr间的近共振振动-振动能量转移

利用简并受激超拉曼泵浦激发HBr(Χ~1Σ~+ν~″=5)振动态,由高分辨瞬时激光感应荧光(LIF)探测碰撞弛豫后HBr(ν~″≤5)各振动态时间分辨布居数的演化过程,得到了HBr(ν~″=5)分别与分子M(H_2,N_2,CO_2和HBr)的碰撞弛豫速率系数。对于M=CO_2,近共振的1-1振动-振动(V-V)能量转移是有效的,这一结果表明CO_2强的红外振动模对近共振V-V能量转移是有利的。而红外禁戒跃迁的N_2(0-1)的近共振V-V转移虽然也能观察到,但相应速率系数比CO_2小2个量级。碰撞分子的振动跃迁红外活性越强,能量转移速率系数越大。在HBr(ν~″=5)+HBr的自弛豫过程中,单量子弛豫率占总弛豫率的70%,而双量子弛豫约占25%。在HBr(ν~″=5)+H_2中,只有2-1的V-V近共振过程是重要的。同时还研究了V-V近共振能量转移速率系数与温度变化的关系,对于CO_2的1-1近共振,V-V能量转移速率系数随温度的增加而减小;对于H_2和HBr,其弛豫速率系数随温度的增加而增加;对于N_2,其弛豫速率系数随温度的增加而缓慢增加。     

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.     

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.     

Multistability of states of a molecular gas with the V-T relaxation time dependent on the vibrational energy

The possibility of realizing multistability of states under the action of IR radiation on a molecule under conditions of nonlinear absorption of light energy and dependence of the V-T relaxation time on its vibrational energy is shown. A two-wave optically bistable arrangement potentially having a highly contrasting range of states is proposed. The nonlinear dependence of the V-T relaxation time on the vibrational energy is shown to allow the realization of optical bistability based on the absorption of light energy at the frequency of the fundamental vibrational transition.     

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.     

Infrared fluorescence from exciting the v1 and v8 modes of CF2Cl2 with a TEA CO2 laser

Infrared fluorescence from CF₂Cl₂ molecules excited with a TEA CO₂ laser below dissociation threshold, is time resolved with a HgCdTe detector without spectral resolution in the range 1100-700 cm^-1. The signal fits well to a sum of three exponentials, which are interpreted as a bulk vibration-vibration (V-V) energy transfer between the fraction of highly excited and non-excited molecules in the irradiated volume, vibro-translation (V-T) deactivation and diffusional heat and mass transport to the surrounding. The measured V-V and V-T rates increase with vibrational excitation and the V-T deactivation is independent on the observed modes (v₁/v₆ or v₈) if v₈ or v₁ are excited respectively.