用发射光谱法测量氮气直流辉光放电的转动温度

本文报道了氮气气压分别为10和20Pa时，对直流辉光放电的发射光谱进行测量和分析的结果。选择的研究对象为N2放电中形成的N2^ B^2∑u^ →X^2∑g^ 跃迁的Δv=v′-v″=0谱带系中v′=0→v″=0谱带的R支。在阴极背面辉光区、阴极鞘层区、正柱区以及阳极辉光区中分别选择一点进行了转动分辨的发射光谱的测量。利用自己编写的光谱拟合程序，获得了相应的实验条件下N2^ 的转动温度，给出了转动温度随放电电压的变化趋势，其结果可以用直流放电的帕邢定律得到很好的解释。在10和20Pa气压下，放电的阴极鞘层区、正柱区、阳极辉光区中的转动温度都随放电电压呈现出了不同的变化趋势，甚至是完全相反的变化趋势。我们认为这是由于气压不同时，放电状态不同所致：气压为10Pa时的放电是正常辉光放电，而气压为时20Pa的放电为反常辉光放电。     

基于辐射法和原子发射光谱法的转炉口火焰温度测量

转炉炼钢的终点控制包括钢水出钢时温度及其成分的控制,炉口火焰能够反映炉内脱碳速率及转炉运行参数等。工业炉燃烧火焰可见光谱段,普遍存在着钾(K)和钠(Na)等碱金属元素的原子发射谱线,利用K的特征谱线相对比值可以计算火焰温度。基于辐射双色法,三色法和谱线相对强度法对转炉口火焰温度进行了测量;数据处理过程中对特征谱线进行了基线拟合提取,小波脊线拟合提取;特征谱线进行了Gauss函数和Lorenz函数拟合。结果表明,辐射测温法对谱线比较敏感,选择合理的波段能够有效,精确地测量火焰温度;采用谱线相对强度法受制于特征谱线的数学模型、谱线的跃迁机率、能级的简并度及火焰的光学厚度,需要分辨率非常高的光谱仪才能进行高温转炉火焰中电子温度的测量。     

基于OH自由基A2∑+→X2∏r电子带系发射光谱的温度测量技术

本文基于OH自由基所固有的分子结构特征,通过分子光谱理论系统地分析和计算了OH自由基A2∑+→X2∏r电子带系发射光谱的谱线跃迁频率、能级分布以及爱因斯坦自发发射跃迁概率等重要参数.同时结合实际的光谱实验,分析了谱线的自然展宽、碰撞展宽、多普勒展宽以及仪器展宽等各种展宽因索对谱线线型的影响,从理论上计算了任意转动温度、振动温度以及谱线展宽条件下OH自由基A2∑+→X2∏r电子带系发射光谱的强度分布,并分析了光谱强度分布与转动温度、振动温度以及谱线展宽的关系,为OH自由基A2∑+→X2∏r电子带系发射光谱测温技术提供理论依据.在实验过程中通过理论计算光谱与实验光谱进行拟合,对氢气燃烧火焰的转动温度和振动温度进行了初步的实验研究.     

基于N+2(B2∑+u→X2∑+g)的电弧等离子体振动温度和转动温度测量

通过光谱诊断系统测量大气压直流氩氮等离子体射流的发射光谱,在光谱紫外波段观察到氮的第一负带系N 2(B2∑ u→X2∑ g),利用N 2(B2∑ u→X2∑ g)跃迁的△v=0谱带系v'=0→v"＝0和v'＝1→v"＝1谱带,对实验测得的谱带和模拟计算得到的谱带进行点对点对比,得到了等离子体射流的振动温度和转动温度,并就仪器展宽、振动温度和转动温度对谱带结构和形状的影响进行了分析.结果表明在文章所述的实验条件下,等离子体的电子温度、振动温度、转动温度和化学动力学温度基本相等,大气压直流氩氮等离子体射流达到局域热力学平衡.     

原子发射光谱双谱线法测量固体火箭发动机内燃气温度

发展了一种利用原子发射双谱线法，测试固体火箭发动机燃烧室内燃气温度的方法，设计了相应的测试系统。该方法利用石英光学纤维，将固体火箭发动机内高温高压燃气的光谱辐射信号传入测量系统；选用了两条波长间隔小的谱线，大大减少了光谱辐射率，光谱透射率等对光谱测量的影响，设计使用了耐压测量探头，保证在高压，强腐蚀条件下，系统的密封性和光的透过率，对装填有SQ－2推进剂的固体火箭发动机燃烧室内的气流温度进行了在线检测，测量时间分辨率可高达0．5μs。     

基于OH自由基A2Σ + →X2Πr 电子带系发射光谱的温度测量技术

本文基于OH自由基所固有的分子结构特征,通过分子光谱理论系统地分析和计算了OH自由基A²Σ ⁺ →X²Π_r 电子带系发射光谱的谱线跃迁频率、能级分布以及爱因斯坦自发发射跃迁概率等重要参数.同时结合实际的光谱实验,分析了谱线的自然展宽、碰撞展宽、多普勒展宽以及仪器展宽等各种展宽因素对谱线线型的影响,从理论上计算了任意转动温度、振动温度以及谱线展宽条件下OH自由基A²Σ ^{关键词： 发射光谱 转动温度 振动温度 自发发射爱因斯坦跃迁概率}     

等离子体发射光谱的诊断及N2振动温度的测量

本文自行设计圆柱形真空管以产生可达几帕的低压环境,并在65 Pa空气和14 Pa的空气-CO₂混合气体直流放电中观测了管轴线上各点的发射光谱,并区分出其中最强的谱带系为N₂的第一正带系和第二正带系,进而利用第二正带系的相对强度计算了两种环境下氮气分子的振动温度沿放电管轴线的分布情况.     

真空电弧等离子体发射光谱诊断

真空断路器的开断容量限制其在高压大电流开断领域的应用,获取燃弧过程中的等离子体参数对于提高真空断路器的开断容量至关重要。利用发射光谱法对真空电弧内的等离子体参数进行了诊断,研究了在不同电流幅值条件下真空电弧内电子温度、电子密度、谱线强度的轴向分布规律,结合真空电弧高速图片对真空电弧内不同粒子的扩散过程与弧柱直径之间的关系进行了分析。得到的电子温度在8000～10 000 K量级,电子密度在10¹⁹～10²⁰ m⁻³量级,电子温度与电子密度从阴极向阳极逐渐下降,同时铜原子谱线强度主要集中在两极而一价铜离子谱线强度由阴极向阳极逐渐升高。铜原子谱线强度的径向分布呈现类平顶波分布、一价铜离子谱线强度的径向分布呈现类高斯分布的特点,且铜原子的谱线范围略大于弧柱直径,一价铜离子的谱线范围略小于弧柱直径,两种粒子的扩散速度存在差异。     

空心针板放电等离子体气体温度和振动温度研究

使用空心针板放电装置,以氩气作为导入气体,在大气环境下产生了1.6~3 cm波长的等离子体炬。利用发射光谱法,研究了等离子体炬弧根和弧梢处的气体温度和振动温度,以及它们随气体流量的变化。等离子体气体温度通过对OH基309 nm附近的谱带进行拟合得到,等离子体振动温度由氮分子第二正带系C3Πu—B3Πg计算得到。实验发现弧根和弧梢处的气体温度相等,并随着气体流量的增大而下降。当气体流量从3.0 mL.min-1增大到6.5 mL.min-1时,气体温度由350 K下降到300 K。当气体流量较小(如3.0 mL.min-1)时,弧梢处的振动温度(1 950 K)高于弧根处的振动温度(1 755 K)。随着气体流量的增大,弧梢处与弧根处的振动温度均下降,但弧梢处下降速率较快。当气体流量较大时,二者趋于相等。     

等离子体针放电的振动温度和气体温度研究

大气压等离子体针空气放电产生的低温等离子体由于脱离了真空装置,在工业上具有广泛的应用前景。本文采用等离子体针装置在空气中产生了稳定的大气压等离子体羽,并利用光谱法对等离子体羽的振动温度和气体温度进行了研究。结果发现大气压空气等离子体羽的放电区域分为强光区和弱光区。放电发光信号是宽度为几个微秒的脉冲。研究结果表明等离子体振动温度随空间位置不同在2 500～3 000K范围变化。振动温度在强光区随着远离针尖距离的增大振动温度呈上升趋势,在5mm左右存在极大值,在弱光区随着远离针尖距离的增大振动温度呈下降趋势。与其相似,弱光区放电的气体温度随着远离针尖距离增大,从640K降低到540K。这些结果对大气压空气放电的工业应用具有重要意义。     

The analysis of nitrogen rotational and vibrational bands in a helium microhollow gas discharge

Emission spectroscopy is applied to measure the gas temperature T _g and the vibrational distribution of N₂ (C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) excited states from a helium microhollow gas discharge (MHGD) at atmospheric pressure. The rotational temperature T _rot of N₂ ⁺ is determined from relative intensity of the R‐branch lines of the N₂ ⁺(B ²Σ_u ⁺–X ²Σ_g ⁺) bands at 427.81 and 419.91 nm and the well‐known Boltzmann plot (BP). Using the same diagnostic technique, the rotationally resolved N₂(C ³Π_u–B ³Π_g) band at 380.49 nm is used to measure T _rot. Under our experimental conditions, T _g is equal to T _rot = 550–650 K for nitrogen molecules and shows a slight increase with the discharge current in the current range 3–10 mA. From the intensity ratio of two consecutive vibrational bands of the same sequence, the N₂(C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) vibrational temperature T _vib = 3,700–4,000 K is determined. It has been found that N₂ ⁺(B ²Σ_u ⁺) ions have non‐Boltzmann distribution in the helium MHGD, while N₂(C ³Π_u) molecules are populated according to the Boltzmann distribution. Following the Franck–Condon principle, the vibrational distribution of the ground state of N₂(X ¹Σ_g ⁺) molecules has been determined from the N₂(C ³Π_u) distribution using the inversion matrix of elements q _XC(ν ,ν ′).     

High-resolution rotational spectroscopy of iminosilylene,HNSi

By means of Fourier transform microwave spectroscopy of a supersonic beam, the fundamental rotational transition of isotopic and vibrationally excited iminosilylene, HNSi, has been detected. In addition to seven isotopic species, vibrational satellite transitions from more than 30 vibrationally excited states, including the three fundamental modes, have been detected. Those from ν₂ are particularly intense, enabling detection of transitions from as high as (0,22⁰,0) (i.e. ～10,000 cm^?1 above ground). At high spectral resolution, well-resolved nitrogen quadrupole structure has been observed in nearly every transition. Excitation of ν₁ or ν₃ changes eQq(N) little, but eQq(N) systematically decreases with increasing excitation of the ν₂ bend, from a value of 0.376(5) MHz for (0,0⁰,0) to ?2.257(5) MHz for (0,20⁰,0). With the large amount of new data in hand, it has also been possible to determine the leading vibration–rotation constants (α_i and γ_i) for ν₂ or ν₃ to high precision, and derive a revised semi-empirical equilibrium structure for this fundamental triatomic molecule. Various electronic and molecular properties of iminosilylene have been calculated at the coupled cluster level of theory, and these generally agree well with experiment and previous calculations. An unsuccessful search for HSiN, a highly polar isomer calculated to lie nearly 3 eV above HNSi, is also reported.     

Rotational and vibrational temperatures measured in a chemiluminescent flame from FTIR Bi2 emission spectra

Rotational and vibrational temperatures of the Bi₂ dimer have been measured in a chemiluminescent flame. Emission spectra of the Bi₂ a³Σ_u⁺(a₁1_u)→X¹Σ_g⁺(X0_g⁺) transition in the near-infrared region were recorded with a FTIR spectrometer. High-resolution spectra of the 0-3, 0-8, 0-9, 2-3, 4-1, 6-0, 6-1, and 7-1 bands served for the determination of the rotational temperature. It was observed that both rotational and vibrational levels are described well by Boltzmann distributions. The average rotational temperature was found to be consistent with the vibrational temperature . The study has shown that such a very heavy molecule as Bi₂ can serve for temperature measurements by optical emission as reported so far only for light molecules.     

H2的振动及转动受激喇曼散射研究

本文研究了不同泵浦光偏振态及氢气气压时,氢的振动及转动受激喇曼散射的竞争效应.在5atm的氢喇曼池中,以波长为532nm的椭偏激光为泵浦源,当椭圆的压缩系数为tg26°～tg32°时,获得了60多条Q(1)和S(1)混合谱线.并在低压氢及线偏或准线偏光泵浦条件下,观察到迄今尚未见报道的受激R(1)喇曼谱线.     

The role of vibrational temperature variations in a pulsed dielectric barrier discharge plasma device

The use of dielectric barrier discharge (DBD) plasmas has become a practical way to carry out surface treatment where precise control of the plasma parameters, such as rotational and vibrational temperatures (T_rot and T_vib), is required. As the T_vib of an atmospheric pressure plasma jet appears to be the most important parameter related to the improvement of surface treatments, in this work, we analysed two methods to increase the values of T_vib in a DBD plasma jet device. One of the methods is to reduce the exit size (ø) of the DBD reactor, which results in an increase in the measured T_vib values, due to an increase in the pressure inside the reactor. The other method is to change the gas flow rate (GFR) used to produce the plasma jets. This leads to a T_vib reduction when the GFR is increased in the case of using helium or nitrogen as the working gas, but the opposite happens (an increase in the T_vib values) when argon is used, with different phenomena causing the variation of T_vib in each situation.     

Non-thermal rotational and vibrational excitation of CN produced in the flash photolysis of thiazole

In the flash photolysis of thiazole at low pressure without any diluent, the 0–0, 1–1 and 0–1 bands of the CN violet system were observed in absorption; the 0–0 band at 3883·4 Å showed a high rotational excitation corresponding to a temperature of ?2000 K. The addition of argon makes the NCS bands appear with good intensity and at the same time relaxes the CN rotationally and vibrationally. These observations suggest that highly excited NCS is initially formed in the photodecomposition of thiazole which acted as a precursor to the rotationally and vibrationally excited CN radical. This paper deals with studies on the effect of argon on the relative intensities of CN and NCS and on the non-thermal rotational and vibrational intensity distribution of the CN violet system. The mechanism of formation of rotationally unrelaxed CN in the flash photolysis of thiazole has been proposed.     

Rotational and vibrational temperatures of electronically excited BiN radicals in a chemiluminescent flame

Rotational and vibrational temperatures of electronically excited BiN radicals in a low-pressure Bi_x+N/N₂*/N₂+Ar chemiluminescent flame have been deduced from high-resolution Fourier-transform emission spectra. Bands of three electronic transitions, a³Σ⁺(a₁1)→X¹Σ⁺(X0⁺), b⁵Σ⁺(b₁0⁺)→X¹Σ⁺(X0⁺), and b⁵Σ⁺(b₁0⁺)→a ³Σ⁺(a₁1), were analysed to determine the optical temperatures in the a³Σ⁺(a₁1) and b⁵Σ⁺(b₁0⁺) states. The rotational temperatures characterising the rotational populations in the a₁1, v=0 and 1 states were determined from the a₁→X, 0-2, 0-3, 0-4, 1-1, and 1-2 bands. The b₁→X, 0-8 and 0-11 bands, and the b₁→a₁, 0-0 bands served to determine the rotational temperature of the radicals in the b₁0⁺, v=0 state. The temperatures derived from the various bands and transitions were well consistent and the mean rotational temperature was determined to be 353±18 K, which is close to the translational temperature of the gas.Vibrational temperatures of the radicals in the a₁1 and b₁0⁺ states were derived from band intensities of the a₁→X and from the b₁→X as well as b₁→a₁ systems, respectively. The Franck-Condon factors needed were calculated with RKR potentials deduced from literature values of the rotational and vibrational constants in the three states involved. The a₁1 vibrational temperature (336±21 K) was close to the rotational temperature, while the b₁0⁺ vibrational temperature (438±36 K) differed, likely due to the previously observed perturbation of the b₁0⁺ state.     

Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states

We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, ν₂₀, ν₃₉, and ν₁₂ have been assigned. The v₂₀ = 1 and v₃₉ = 1 states are near 100 cm⁻¹ in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (ΔE/hc)=10.400222(5) cm⁻¹. A newly developed software package for assignment and analysis of broadband spectra is described and made available.