Study of nonlinear light scattering in water in the region of the second optical harmonic of laser radiation

The frequency-angular spectrum of nonlinear light scattering in water in the region of the second optical harmonic of picosecond Nd³⁺YAG laser radiation is studied. It is shown that this scattering occurs by the four-photon interaction mechanism. Statistical treatment of the spectra of four-photon scattering in the collinear interaction mode revealed a structure related to the frequency of infrared radiation caused by vibrations of cluster complexes of water molecules.     

基于HITRAN数据库的深海甲烷辐射光谱仿真研究

研发能够精确、实时、原位获取热液甲烷数据的深海甲烷传感器对深海研究具有非常重要的意义。前期研制的两款深海甲烷光学成像干涉系统,均利用甲烷辐射光谱开展甲烷状态参数探测和反演。首先,以分子光谱辐射理论为基础,建立了分子辐射光谱与浓度、温度、压强的理论关系式,结合深海高压环境特点,建立了基于Lorentz线型的深海分子辐射模型,该模型为利用光谱法定量反演分子浓度、温度、压强等状态参数提供理论依据,同时为深海分子光谱仿真提供有力工具。接着,借助HITRAN分子光谱数据库提供的分子基本谱线参数,挑选出甲烷成像干涉系统的光源谱线。对比CH₄分子与CO₂, H₂S, H₂O等分子的特征吸收谱线,在5 990～6 150 cm-1波段范围内,CH₄谱线强度比CO₂, H₂S, H₂O等三种干扰分子的谱线强度约高2～3个数量级,且此波段内甲烷六条有效谱线分布均匀,谱线间距皆约为2～3 nm,非常适合采用光谱法进行分子状态参数探测,因此选择谱线干扰较弱、谱线分布均匀、谱线间距适中的甲烷六条谱线(1 640.37, 1 642.91, 1 645.56, 1 648.23, 1 650.96和1 653.72 nm)作为甲烷成像干涉探测系统的目标光源谱线。最后,基于深海分子辐射模型和HITRAN数据库的甲烷分子基本谱线参数,人工合成了甲烷任意浓度,任意温度和任意压强的辐射光谱数据,并分析了甲烷辐射光谱随浓度、温度和压强的变化特征。对于单一中心谱线,甲烷分子辐亮度随着浓度的升高而线性增大,随着温度的升高而非线性增大,随着压强的升高而非线性减小。对于全波段谱线,甲烷辐射光谱的全线宽随着浓度、温度的升高而变宽,随着压强的升高而变窄。建立的深海甲烷辐射光谱理论和仿真分析结果,可以为基于光谱法的海洋原位甲烷传感器的研制和数据反演提供数据支撑和理论依据。     

基于页岩气返排液中甲烷浓度及排放速率的红外光谱反演研究

随着页岩气的开发,传统的手持式甲烷测量仪无法继续应对复杂的开采工况。针对页岩气开发过程中温室气体甲烷的浓度及排放速率难以实时在线监测的问题,利用自主设计并搭建的开放光程傅里叶变换红外光谱（FTIR）测量系统,对页岩气开采过程中各种工况下返排液进行实时在线测量。其中FTIR分辨率为1 cm-1, 光程为50 m,红外光源通过返排液正上方被光谱仪接收。对测量所得的红外光谱进行多次平均,提高光谱质量并进行反演计算。从HITRAN数据库中提取甲烷特征吸收截面,考虑环境与仪器等影响,对测量温度进行修正,选取合适的吸收波段,与水汽的吸收截面进行吸收峰叠加,合成标准光谱。使用最小二乘法对实测光谱与标准光谱进行拟合,从而反演出甲烷浓度。并根据返排液排放速率,结合光路通过返排池的距离及红外光谱反演浓度,对页岩气开采过程中甲烷排放速率进行计算。结果表明：不同开采工况下,光谱反演浓度呈明显起伏变化。更换三项分离器时,甲烷浓度有明显上升;在点燃火炬时,甲烷浓度持续低值;其红外光谱反演浓度符合页岩气开采过程中甲烷排放情况。改变测量光谱平均次数,对返排液甲烷进行单位小时和连续80小时测量并分析。在单位小时内,甲烷浓度在100～800 μmol·mol-1范围内呈现明显起伏变化;甲烷的排放速率在50～300 m3·h-1内波动。对返排液进行80小时连续测量,甲烷浓度最大值为936.4 μmol·mol-1,其最大排放速率达到535.1 m3·h-1;最低值为36.82 μmol·mol-1最小排放速率为18.63 m3·h-1。反演数据结果说明：在页岩气开发过程中,其返排液为一个无组织甲烷排放源,且排放速率在短时间内变化十分明显。红外光谱反演浓度和传统手持式甲烷测量仪测量结果具有较好一致性,相关系数为0.743 6。相对于传统手持式甲烷测量仪器,红外光谱反演法具有响应速度更快,非接触远距离,实时在线测量等优势。     

Computer simulation of the cluster destruction of stratospheric ozone by bromine

The interaction of(Br-)i(H2O)50-i,0≤i≤6 clusters with oxygen and ozone molecules is investigated by the method of molecular dynamics simulation.The ozone molecules as well as the bromine ions do not leave the cluster during the calculation of 25 ps.The ability of the cluster containing molecular oxygen to absorb the infrared(IR) radiation is reduced in the frequency range of 0≤ω≤3500 cm-1 when the number of the bromine ions in the cluster grows.The intensity of the Raman spectrum is not changed significantly when the Br-ions are added to the ozonecontaining system.The power of the emitted IR radiation is increased when the number of bromine ions grows in the oxygen-containing system.The data obtained in this study on the IR and the Raman spectra of the water clusters that contain ozone,oxygen,and Br-can be used to develop an investigation of the mechanisms of ozone depletion.     

热氧喷嘴水煤浆扩散火焰辐射光谱特性研究

火焰的辐射光谱可为燃烧诊断提供诸多信息,因此目前对简单的气态火焰自由基辐射特性已进行了大量研究,而关于非均相火焰的辐射光谱特性研究则相对较少。采用改进的热氧喷嘴技术在敞开空间下直接点燃水煤浆,并利用光纤光谱仪和紫外成像系统,着重对甲烷和水煤浆火焰的辐射光谱及OH*的二维分布特性进行研究。结果表明：与甲烷火焰的光谱辐射相比,水煤浆火焰不仅存在OH*,CH*和C₂*特征辐射,还产生了Na*,Li*,K*和H*的发射谱线,并出现了连续的黑体辐射,这些光谱辐射特征可作为水煤浆气化或燃烧的标志,也可作为水煤浆是否点燃的判据;通入水煤浆后,OH*强度明显下降,而CH*和C₂*强度增大。对比甲烷火焰OH*二维分布,水煤浆火焰OH*峰值强度明显下降,化学反应区域面积显著减小;沿着火焰传播方向,甲烷和水煤浆火焰轴向的OH*强度均呈先增大后减小的趋势;甲烷火焰径向的OH*在反应核心区出现了双峰形态分布,而水煤浆火焰OH*径向始终呈单峰分布。随着氧碳当量比增大,水煤浆火焰OH*的存在范围扩大,说明氧气的增加促进了OH*的产生;随水煤浆流量提高,OH*的反应核心区域缩小,峰值强度明显下降,CH*,C₂*,Na*,Li*,K*和H*的强度显著增强,连续的黑体辐射强度也明显增大,这些辐射光谱的变化可用于表征操作负荷的变化。     

纳秒激光诱导空气等离子体的红外辐射特性研究

纳秒激光诱导空气等离子体存在从紫外、可见、近红外乃至射频微波的宽谱段辐射,但目前的研究大多关注紫外到可见波段的光谱辐射。激光等离子体作为一种新型的红外辐射源具有很多优势,相比于红外干扰弹以及红外干扰手段而言,空气等离子体红外辐射源可以灵活布置,成本低廉,因此研究空气等离子体的红外辐射特性就很有必要。针对目前脉冲激光诱导空气等离子体的红外干扰研究需要,对激光波长为532 nm的纳秒脉冲激光诱导空气等离子体的红外辐射特性进行实验研究,探讨激光能量对空气等离子体红外辐射强度的影响规律,以及空气等离子体红外辐射的角度分布特性,分析了等离子体红外辐射的可能产生机制。实验结果表明,激光诱导空气等离子体在950～1 700 nm范围内的红外光谱为线状谱和连续谱的叠加。其中线状谱主要是氮和氧的中性原子谱线,并且氮原子红外辐射占主导。随着激光能量的增加,由于空气击穿产生的氧和氮原子数量增加,导致空气等离子体红外辐射的谱线强度逐渐增大。随着红外探测角度的变化,在探测角度为75°时,OⅠ 1 128.63 nm和NⅠ1 246.96和1 362.42 nm谱线强度达到最大,在探测角度为120°时,NⅠ 1 011.46和1 053.96 nm谱线强度达到最大,这是因为空气等离子体红外辐射强度随探测角度变化呈现空间非对称性,表明空气等离子体内不同粒子的空间分布呈现非对称性。     

3 016.49 cm-1波数下变气压、温度的甲烷吸收系数计算研究

红外甲烷传感器根据朗伯-比尔定律对甲烷的浓度进行检测,而吸收系数是朗伯-比尔定律中的重要参数,其受温度和压强的影响变化较大,其变化会导致浓度测量的误差,因而研究不同温度、气压下甲烷吸收系数的变化规律对设计高精度的红外甲烷传感器有重要意义。文献报道中,一般采用获得测量甲烷浓度受环境影响的实验数据,再加以数学处理的方法,对测量误差进行补偿和修正。该工作以分子光谱分析理论为基础,以3 016.49 cm-1波数的甲烷为研究对象,利用HITRAN数据库的甲烷数据,设计了Python程序调用HAPI函数,拟合计算出甲烷吸收系数随温度、气压的变化规律,并通过傅里叶红外光谱对甲烷吸收系数的变化规律进行实验验证。结果表明,在3 016.49 cm-1处,水分子（湿度的影响）对于甲烷吸收系数的影响很小,可以忽略不计;温度和气压对吸收系数有一定的影响,当气压为1.0 atm,温度在-10～50 ℃范围内升高时,甲烷吸收系数减小,吸收系数与温度的关系呈线性关系;当温度为273.15 K时,气压在0.6～1.2 atm升高时,甲烷收系数增加,吸收系数与气压关系呈线性关系。最后拟合出的吸收系数与温度、气压的公式,k(T, p)=53.65(±3.24)-0.114 6(±0.010 7)T+21.07(±0.95)p。实验中甲烷标准气体的浓度分别为1.01%,2.00%,3.51%和5.06%,通入直径为2.5 cm,长度为8 cm的短光程石英气体池中,通过改变气体的气压及温度,从傅里叶红外光谱仪获得甲烷的吸光度,由于受实验仪器分辨率的影响,如直接通过吸光度反演甲烷浓度其误差较大,采用吸收系数与吸光度的比值来判断吸收系数拟合的正确性。结果表明,浓度为定值,气压与温度变化时,吸收系数与吸光度之比基本为定值,从而证明了计算拟合出的甲烷吸收系数随温度压强变化的正确性。     

Variability of the terrestrial window and its physical implications

Summary We show that the frequencies of atmospheric molecular thermal vibrations significantly influence the spectral positioning of the terrestrial window. The bandpass filtering process of this window is confined to the region starting from theE-region and extending to an altitude not exceeding about 600 km. This indicates that a significant part of the infrared radiation emanating from lower altitudes is absorbed directly into the ionosphere. Implicitly, the infrared radiation field as viewed downward from the top of the ozonosphere is continuously ?mapped? into the ionosphere in terms of temperature and hence ionization variations. This mapping may be a vital cause of ionospheric irregularities. Factors that influence the transmission coefficient of the terrestrial window are mentioned and discussed. In particular, it is shown that if the terrestrial thermal radiation shifts in response to a temperature change in accordance with Wien's displacement law, the terrestrial window cannot correspondingly shift and continue aligning itself approximately with the peak of the spectrum unless different atmospheric molecules dominate the vibrational process. However, whether different molecules dominate the vibrational process or not, a change in atmospheric temperature makes the transmission coefficient of the window change in the same sense. Consequently, the much reported role played by the window in moderating the temperature of the Earth-Atmosphere system is apparently carried out even when the latter temperature changes provided that the accompanying adjustments do not put the spectral location of the window completely off the terrestrial radiation spectrum. Finally it is shown that if certain substances are introduced in sufficient quantities into the troposphere (in gaseous or aerosol forms), the bandpass filtering process of the terrestrial window may consequently operate in the latter and hence cause regional or global warming.     

Estimation of electromagnetic energy accumulation time in a water drop exposed to infrared laser radiation

The time of accumulation of electromagnetic energy in a water drop exposed to infrared laser radiation is estimated numerically taking into account the energy of interaction of water molecules and optical parameters of the water drop. The calculated value of electromagnetic energy accumulation time is in good agreement with the experimental value.     

An investigation of the infrared spectra of melt water at room temperature

It was shown experimentally that the infrared spectra of melted and never-frozen distilled water differed at frequencies of 1640 and 2130 cm^?1. This is explained by the long relaxation of water molecules structures to an equilibrium state in melt water. It was suggested that near the frequency 2130 cm^?1 there was a bigger influence of dissolved gas relaxation on the value of the transmitted intensity of infrared radiation than near the 1640 cm^?1 line.     

闪电放电通道的辐射演化特性

用无狭缝红外光谱仪获得了山东地区云对地闪电回击过程的近红外光谱,并与可见光波长范围的闪电回击光谱进行了对比分析.根据近红外光谱的结构特征,讨论了闪电通道等离子体的光谱辐射顺序以及不同波段连续光谱的主要辐射机制,研究得出：可见光谱主要是闪电回击初期和发展阶段的辐射|近红外光谱主要是闪电发展后期的辐射|可见波段的连续光谱主要来自韧致辐射的贡献,而红外部分的连续光谱主要来自复合辐射的贡献.由分析结果推断：闪电通道等离子体的复合过程是闪电产生O3、NOX的主要途径,复合过程中的氧吸附作用和去吸附过程是近红外光谱中氧原子谱线增多的重要原因,也是OI 777.4 nm相对强度比较大的主要原因.     

Radiative transfer within the atmospheres of the major planets

A modified Eddington approximation is presented which describes radiative transfer due to the pressure-induced far infrared spectrum of hydrogen. When applied to the atmospheres of the major planets, the radiative transfer model produces atmospheric temperature profiles which are in good agreement with more detailed calculations. Solar absorption and infrared transmission by the fundamental bands of methane are further included for Jupiter and Saturn, resulting in a temperature inversion within both atmospheres above an altitude corresponding to a pressure of roughly 0.01 atm. This relatively high inversion region appears to be qualitatively consistent with infrared observations of methane and ammonia bands for Jupiter. Additional sources of solar absorption, consisting of the pressure-induced vibration-rotation bands of hydrogen and the overtones of the v₃ methane fundamental, are shown to have a minor effect upon the atmospheric thermal structure for Jupiter and Saturn.     

Infrared spectra of carbon monoxide on evaporated nickel films: A low temperature thermal detection technique

A novel thermal detection scheme has been developed and combined with the techniques of rapid scan Fourier transform infrared spectroscopy to make sensitive, high resolution measurements of the vibrational spectrum of carbon monoxide molecules on evaporated nickel films. Adsorbed molecules are detected by attaching a germanium resistance thermometer to the sample, cooling the assembly to liquid helium temperatures, and measuring the temperature changes which occur when infrared radiation is absorbed. Spectra are presented for a range of CO coverages on an evaporated nickel film and a film damaged by ion bombardment. The positions, shapes, and intensities of the spectral lines from linear and bridge bonded CO molecules give information about the surface structure of the metal films and about the different ordered phases of the adsorbed molecules.     

基于图像的飞行器红外辐射特性测量

通过将目标在一定波段内的红外辐射等效为红外成像系统前一定距离下黑体在对应波段内的红外辐射,建立了等效辐射方程。根据黑体辐射定标实验数据,利用非线性回归方法确定了在不同的积分时间条件下红外凝视成像系统输出红外图像的灰度值与在一定距离下的黑体温度之间的定量关系,建立了辐射定标方程。在Visual C++6.0平台下,在对红外目标图像进行SUSAN滤波等预处理后,分析了已知目标距离的红外图像的灰度均值。首先根据辐射定标方程计算出目标等效为黑体的温度,然后利用等效辐射方程反推目标的红外辐射强度,以达到根据跟踪的红外图像确定红外目标辐射特性的目的。此项研究不仅可以为目标识别提供目标分类、识别和辨认所必需的光谱数据库,而且还可以为红外预警提供重要的参考数据。     

Generation of tunable infrared radiation in rubidium titanyl phosphate crystal for the optical measurement of number density, absorption cross-section of methane gas

Tunable near-infrared radiation has been generated in a rubidium titany1 phosphate (RTP) crystal by employing non-collinear difference-frequency mixing (DFM) technique. The input radiation sources are Nd:YAG laser radiation and its second harmonic pumped dye laser radiation. For the generation of 2.0 radiation, the maximum value of the conversion efficiency (quantum) obtained in the process is 49% from the dye (0.6945 μm) to the infrared (2.0 μm) radiation in the 7.9-mm-long crystal. The generated tunable mid-infrared radiation has been used to measure the number density, absorption cross-section and minimum detectable concentration of methane gas in its 2ν₃ band in a multi-pass cell at 30.075 Torr pressure. The number density and column density of the methane molecules are found to be 1.068×10¹⁸ cm⁻³ and 3.02×10²¹ cm⁻², respectively, whereas the minimum still-detectable concentration at 1.658 μm wavelength is estimated to be 4.523×10¹⁷/cm³.     

醇类抑制剂对甲烷水合物形成的影响

在本工作中,甲烷水合物的生长动力学是通过甲醇、乙醇、乙二醇三种不同醇类抑制剂存在下的分子动力学模拟研究的.模拟结果发现,三种醇类都可作为甲烷水合物的抑制剂,醇类分子中的亲水性羟基极大地破坏了水合物笼的结构,并且羟基可以与局部的液态水分子形成氢键,从而增加了形成水合物笼型结构的难度,导致甲烷水合物的生长速率降低.对于甲醇分子,甲醇分子的亲水性羟基与水分子形成氢键从而破坏了水分子结构,而亲油性甲基对周围的水分子具有簇效应,两者都会降低水合物生长速率;对于乙二醇和乙醇分子,它们只含有羟基,特别是乙二醇分子含有两个羟基,其对H₂O分子有很强的吸附作用,导致水合物生长速率降低.在抑制效果方面,甲醇分子最优,乙二醇稍微优于乙醇.     

电场作用下P掺杂硅烯选择性吸附CH_4的第一性原理计算

在煤层气中选择性吸附和捕捉甲烷分子,对提高煤矿安全具有十分重要的意义.本文采用第一性原理计算的方法,研究了外加电场作用下P掺杂硅烯对甲烷分子的选择性吸附性能.结果表明:正电场作用下,P掺杂硅烯与甲烷分子之间产生较强的化学吸附,能够快速捕获甲烷分子.当关闭外加电场时,P掺杂硅烯与甲烷分子之间则为微弱的物理吸附,甲烷分子很容易实现脱附.同时还发现,外加电场作用下,P掺杂硅烯与氮气、氧气及水之间的吸附均属于物理吸附,表明P掺杂硅烯可以在这些混合气体中实现甲烷气体的选择性吸附. P掺杂硅烯有望成为选择性好的甲烷传感、捕获新材料.     

不需干燥预处理过程获得含水汽的丙酮气体样品的高质量红外光谱

测量气体样品的红外光谱时,红外光谱仪器内的水汽和气体样品中所含的水汽会严重干扰气体的红外光谱。为消除水汽的干扰,通常作法是测量前必须将水分子(气态)彻底排除掉,也就是使光谱仪器和气体样品保持干燥状态。该研究提供一个新测量方法,不需任何干燥预处理过程,直接获得含水汽的丙酮气体的红外光谱。经过几十次光谱扫描累加后,观察并根据水汽谱的吸收峰性质(吸光率>0或吸光率<0),向光谱仪样品室引入少量干燥氮气或少量潮湿空气,在接下来的光谱扫描累加过程中,水汽吸收峰将逐渐变小直至消失。实验结果表明该方法去除水汽干扰峰简单高效。新方法在0.5 cm-1光谱分辨率时效果非常好,为气体的高分辨分析提供了有力工具。     

辐射背景对岩石受力热红外光谱变化影响的实验研究

研究表明,岩石在加载过程中表面的红外辐射随应力发展而变化,而辐射信息的有效提取与辐射背景存在密切关系。通过理论分析不同实验环境对岩石受力热红外光谱变化影响,开展了花岗岩在室内外环境下的受力热红外光谱观测实验,分析了不同辐射背景下岩石红外辐射与应力的相关性以及由应力引发的辐射变化信息的强弱差异,并对两种环境下岩石应力热红外探测的优势波段进行了对比分析。结果表明,辐射背景对岩石受力热红外光谱探测结果有重要影响,室外环境因背景辐射较弱,相同应力作用下的红外辐射变化更加显著,与应力之间的相关程度更高,优势波段区间更宽,更加有利于岩石应力的热红外探测。8.0~11.8 μm波段是利用热红外遥感监测地表花岗岩应力变化的优势波段。     

Infrared spectra of catalysts and adsorbed molecules

The infrared absorption spectra of water adsorbed on Al₂O₃ and NiO-Al₂O₃ catalysts have been studied in the range 4000–1200 cm^–1. For all the catalysts, broad bands are observed at 3400 and 1640 cm^–1, characteristic of the stretching and bending vibrations of the OH groups in liquid water. The bands observed in the spectrum of alumina prepared from suspension in isopropyl alcohol are produced by water molecules and isopropyl alcohol molecules absorbed on the catalyst surface. The influence of treatment with heavy water and thermal treatment on the position of the infrared absorption bands in the spectrum of alumina is discussed.