Diagnosis of negative hydrogen ions and rovibrational distribution of H<Subscript>2</Subscript> molecule in non-thermal plasmas

Rovibrational excited hydrogen molecule plays an important role for the production of H^- ions. The correlation between H^- ion density and rovibrational distribution of H₂ molecules has been investigated in dielectric barrier discharge hydrogen plasmas via optical emission spectrometry and molecular beam mass spectrometry. The relative vibrational distribution of molecular hydrogen in the electronic ground state has been determined by the best fitting to the Fulcher-α band emission lines. It is shown that the ratio of the Q_(0-0)(1) to Q_(1-1)(1) line is very suitable and simple for the diagnosis of vibrational temperature in the range of 1500 to 7500 K. At certain discharge conditions (ac 40 kHz, 14 kV), the vibrational temperature decreases from 3600 to 2400 K as the pressure increases from 100 to 200 Pa and the negative ions density near the ground electrode also decreases as the pressure increases. Both the hydrogen ions density and the vibrational temperature increase with the increasing of discharge voltage. It is found that the evolution of negative atomic hydrogen ions density greatly depends on the vibrational temperature.     

Performance of non-thermal DBD plasma reactor during the removal of hydrogen sulfide

Destruction of hydrogen sulfide using dielectric barrier discharge plasma in a coaxial cylindrical reactor was carried out at atmospheric pressure and room temperature. Three types of DBD reactor were compared in terms of specific energy density (SED), equivalent capacitances of the gap (Cg) and the dielectric barrier (Cd), energy yield (EY), and H₂S decomposition. In addition, byproducts during the decomposition of H₂S and destruction mechanism were also investigated. SED for all the reactors depended almost linearly on the voltage. In general, Cg decreased with increasing voltage and with the existence of pellet material, while Cd displayed the opposite trend. The removal efficiency of H₂S increased substantially with increasing AC frequency and applied voltage. Longer gas residence times also contributed to higher H₂S removal efficiency. The choice of pellet material was an important factor influencing the H₂S removal. The reactor filled with ceramic Raschig rings had the best H₂S removal performance, with an EY of 7.30 g/kWh. The likely main products in the outlet effluent were H₂O, SO₂, and SO₃.     

Generation of VUV radiation in Lyman and Werner bands of pulsed space discharge in hydrogen mixtures with helium

A self-consistent numerical model for the self-sustained high-current pulsed discharge is constructed based on the solution of the equations of the population of H₂ electronic and vibrational states. The model accounts for electronic, ion-molecular, and vibrational kinetics, electron attachment to and detachment from the H₂ molecule, Lyman and Werner band emission, and their radiation trapping. The equations of electron-vibrational kinetics are solved simultaneously with the Boltzmann equation for the electron energy distribution function and the external electrical circuit equations.     

大气压下氮气介质阻挡微放电中分子振动温度的时间分辨

使用针-板式电极装置,在大气压氮气介质阻挡微放电中,通过对氮分子第二正带系(C3Πu→B3Πg)发射光谱的时间分辨谱线进行分析,根据振动带序发射光谱强度计算得出N2(C,ν)振动温度,并研究了不同压强及放电电压对氮分子(C3Πu)的振动温度时间分辨的影响。实验结果表明:氮分子振动温度的范围为2 000~3 500 K,在每半个放电周期内都呈减小趋势,且正负半周期振动温度差较大,负半周期振动温度始终高于正半周期;振动温度随电压升高而升高,随压强的升高而降低。     

Understanding the reaction between muonium atoms and hydrogen molecules: zero point energy,tunnelling, and vibrational adiabaticity

The advent of very precise measurements of rate coefficients in reactions of muonium (Mu), the lightest hydrogen isotope, with H₂ in its ground and first vibrational state and of kinetic isotope effects with respect to heavier isotopes has triggered a renewed interests in the field of muonic chemistry. The aim of the present article is to review the most recent results about the dynamics and mechanism of the reaction Mu+H₂ to shed light on the importance of quantum effects such as tunnelling, the preservation of the zero point energy, and the vibrational adiabaticity. In addition to accurate quantum mechanical (QM) calculations, quasiclassical trajectories (QCT) have been run in order to check the reliability of this method for this isotopic variant. It has been found that the reaction with H₂(v=0) is dominated by the high zero point energy (ZPE) of the products and that tunnelling is largely irrelevant. Accordingly, both QCT calculations that preserve the products’ ZPE as well as those based on the Ring Polymer Molecular Dynamics methodology can reproduce the QM rate coefficients. However, when the hydrogen molecule is vibrationally excited, QCT calculations fail completely in the prediction of the huge vibrational enhancement of the reactivity. This failure is attributed to tunnelling, which plays a decisive role breaking the vibrational adiabaticity when v=1. By means of the analysis of the results, it can be concluded that the tunnelling takes place through the ν₁=1 collinear barrier. Somehow, the tunnelling that is missing in the Mu+H₂(v=0) reaction is found in Mu+H₂(v=1).     

Vibrational spectra of H2O and CF4 molecules using Lie algebraic approach

In this paper, we introduce one dimensional vibron model to analyze the fundamental, overtone and combination modes of CF₄ molecule and both stretching, bending vibrational mode of bent H₂O molecule up to first overtone with few algebraic parameters. Using the model Hamiltonian, we reported here better results for the vibrational spectra of H₂O. Our analysis suggests some reassignments of levels and predicts location of states in case of CF₄ molecule which was not yet observed.     

Lifetimes of the electronic-vibrational-rotational states of hydrogen molecule (Review)

Data on the lifetimes of the vibrational-rotational levels of the excited electronic states of hydrogen molecule (including H₂, D₂, HD, DT, and T₂ isotopomers) are reviewed. All data on the rotational sublevels of the lowest vibrational levels of various electronic states are presented, which were available before June 2001. A comparative analysis of the data obtained by various researchers using different methods (experimental, semi-empirical, and non-empirical) is performed for the first time. The influence of non-adiabatic intramolecular interactions on the dependence of lifetimes of the rovibronic levels of hydrogen molecule on the vibrational and rotational quantum numbers is discussed. A set of reliable data is selected which can be recommended for use in various applications.     

Absorption coefficients for hydrogen—III. calculated pressure-induced H2-H vibrational absorption in the fundamental region

The coefficient for absorption during H₂-H collisions was calculated for temperatures from 2000 to 7000 K and wave numbers between 100 and 40 000 cm^-1 for LTE. Because only transitions with Δν = 1 were considered, the absorption was near the fundamental at 4161 cm^-1 in the infrared. The model included mechanical anharmonicity, vibration-rotation interaction, excited vibrational states, and transverse components of the dipole moment. At 5500 cm^-1, 3750° K, and 1 atm pressure, inclusion of H₂-H vibrational absorption increased the absorption of pure hydrogen gas 48 per cent. An approximate formula for the H²-H absorption coefficient is given for rapid calculation.     

Rotational and Vibrational Temperature Measurements in a High‐Pressure Cylindrical Dielectric Barrier Discharge (C‐DBD)

The rotational (T_R) and vibrational (T_v) temperatures of N₂ molecules were measured in a high‐pressure cylindrical dielectric barrier discharge (C‐DBD) source in Ne with trace amounts (0.02 %) of N₂ and dry air excited by radio‐frequency (rf) power. Both T_R and T_v of the N₂ molecules in the C ³Π_u state were determined from an emission spectroscopic analysis the 2^nd positive system (C ³Π_u → B³Π_g). Gas temperatures were inferred from the measured rotational temperatures. As a function of pressure, the rotational temperature is essentially constant at about 360 K in the range from 200 Torr to 600 Torr (at 30W rf power) and increases slightly with increasing rf power at constant pressure. As one would expect, vibrational temperature measurements revealed significantly higher temperatures. The vibrational temperature decreases with pressure from 3030 K at 200 Torr to 2270 K at 600 Torr (at 30 W rf power). As a function of rf power, the vibrational temperature increases from 2520 K at 20 W to 2940 K at 60 W (at 400 Torr). Both T_R and T_v also show a dependence on the excitation frequency at the two frequencies that we studied, 400 kHz and 13.56 MHz. Adding trace amounts of air instead of N₂ to the Ne in the discharge resulted in higher T_R and T_v values and in a different pressure dependence of the rotational and vibrational temperatures. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Numerical simulations of hydrogen detonations with detailed chemical kinetics

Time-dependent, multidimensional simulations of unstable propagating detonations were performed using a detailed thermochemical reaction model for a stoichiometric argon-diluted hydrogen–oxygen mixture at low pressures and a hydrogen–air mixture at atmospheric pressure. Detonation cells computed for the low-pressure, dilute H₂–O₂–Ar systems were regular in shape, and their sizes compared reasonably well with experimental observations. The computed H₂–air cells at atmospheric conditions were qualitatively different from those observed in experiments, and their widths range from less than 1 mm to nearly 5 mm with multilevel hierarchal structures. The effective activation energy of the H₂–air mixture, based on constant-volume ignition delay times computed using the detailed thermochemical model, varies between 5 and 40 over the range of post-shock temperatures and pressures in the simulations and is, on average, significantly larger than expected based on the regularity of experimental cellular patterns. Analysis of the simulations suggests that vibrational relaxation of the gas molecules, a process which is ignored when calibrating detailed chemical reaction models, occurs on time scales similar to the ignition delay times for the detonations and may be a source of discrepancy between numerical and experimental results.     

HF-laser performance of CO2-laser-ignited mixtures of SF6 :H2 and of S2F10 :H2

We have used a CO₂ laser to ignite mixtures of SF₆ :H₂ and S₂F₁₀ :H₂. We observed HF lasing from these mixtures when an optical resonator was constructed around the reaction cell. The HF-lasing performance of the two mixtures was compared as a function of mixture ratio, fluorine-donor pressure, and CO₂-laser frequency. Under comparable conditions, the HF-laser output for S₂F₁₀ :H₂ mixtures was typically 5–6 times greater than that for SF₆ :H₂ mixtures. Spectral output of the HF laser was coarsely resolved to provide data about the vibrational and rotational states of the HF molecule.     

Intensification of shock-induced combustion by electric-discharge-excited oxygen molecules: numerical study

Mechanisms of combustion enhancement in a supersonic H₂–O₂ reactive flow behind an oblique shock wave front are investigated when vibrational and electronic states of O₂ molecule are excited by an electric discharge. The analysis is carried out on the base of updated thermally nonequilibrium kinetic model for the H₂–O₂ mixture combustion. The presence of vibrationally and electronically excited O₂ molecules in the discharge-activated oxygen flow allows to intensify the chain mechanism and to shorten significantly the induction zone length at shock-induced combustion. It makes possible, for example, to ignite the atmospheric pressure H₂–O₂ mixture at the distance shorter than 1 m behind the weak oblique shock wave at a small energy E_s = 1.2 × 10^–2 J · cm^–3 input to O₂ molecules. At higher pressure it is needed to put greater specific energy into the gas in order to ignite the mixture at appropriate distances. It is shown that excitation of O₂ molecules by electric discharge is much more effective for accelerating the hydrogen–oxygen mixture combustion than mere heating the gas.     

Spontaneous radiative dissociation in molecular hydrogen

The spontaneous radiative dissociations of the discrete vibrational levels of the B¹Σ⁺_u electronic states of H₂, HD and D₂ of the C¹Π_u electronic state of H₂ into the vibrational continuum of the ground X¹Σ⁺_g state are calculated as a function of the emission wavelength. The fluorescent spectra of HD in the Lyman system and of H₂ in the Werner system resulting from an excitation source uniform in wavelength are predicted. The vibrational radiative lifetimes are tabulated as are the fractions of radiative decays that lead to dissociation. The effects of centrifugal distortion are discussed briefly. An appendix describes a sum rule used to check the numerical accuracy of the calculations.     

Theoretical and experimental analysis on spectral,hyperpolarizability and dielectric properties of semi-organic nonlinear optical crystal: Potassium boromalate hydrate (PBH)

Semi-organic potassium boromalate hydrate KBC₈H₈O₁₀·H₂O (PBH) salt was synthesized by reflux method and grown as single crystals by slow evaporation technique. The single crystal X-ray diffraction, Fourier transform infra red (FT-IR) and Fourier transform Raman spectral analyses were carried out to confirm the grown crystals. The factor group analysis was performed and the possible vibrational modes were predicted for PBH. The first order hyperpolarizability value calculated by quantum chemical calculations is well supported by the results obtained from Kurtz–Perry powder technique. The transparency in the entire blue, green and IR region makes it a valid candidate for the NLO applications. From the dielectric studies it is inferred that conductance predominates at low frequency region due to the exchange of electrical charges at crystal surface which results in the local displacement of electrons in the direction of the applied field.     

O3+与H2碰撞中非解离电荷转移过程的全量子计算

应用全量子的分子轨道强耦合方法,研究了基态的O³⁺(2s²2p ²P)与氢分子碰撞的非解离电荷转移过程,计算了不同方位角(25°,45°,89°),能量分别为100,500,1000和5000eV/u时的单电子俘获的振动分辨的态选择截面及相应的微分截面.分子轨道强耦合计算中采用了自旋耦合价带理论计算的三原子分子势能面和径向耦合矩阵元.对氢分子的自身转动,采用无限阶的冲量近似方法;对体系的电子运动同H₂或H^{+< 关键词： 非解离电荷转移过程 全量子的分子轨道强耦合方法 无限阶冲量近似 振动冲量近似国家自然科学基金(批准号：10604011 10574020)和国家高技术研究发展计划(863)惯性约束聚变领域资助的课题.}     

Determination of gas temperature of high-frequency low-temperature electrodeless plasma using molecular spectra of hydrogen and hydroxyl-radical

In this study we determine gas temperature of He+H₂, Ar+H₂ and Ne+H₂ high frequency electrodeless lamps using intensity distribution in rotational spectra of hydrogen molecule and hydroxyl radical. The measurement results show that OH rotational spectra can be successfully used for estimation of gas temperature of the high-frequency electrodeless lamps at very small amounts of hydrogen present in plasma. The analysis of the measurement results leads to the conclusion that in “pure” plasma the applied energy is used to heat plasma, while for the plasma with hydrogen addition the energy is used in chemical reactions.     

Vibrational intensity distributions in the photoelectron spectrum of hydrogen

The intensity distribution over the H₂⁺ vibrational levels up to v = 15 has been measured for H₂ photoelectron spectra at a photon wavelength of 584 Å. The data show reasonable agreement with recent calculations only in the range v = 0 through 8; the higher levels are populated significantly lower than predicted by theory.     

Calculation of the relaxation parameters of overlapping lines of the ammonia molecule pressure broadened by argon and helium

Broadening coefficients γ and interference coefficients ξ are calculated for different bands of the ammonia molecule in the case of line broadening by the pressure of argon and helium. A model intermolecular potential is used. It is shown that taking into account the interference effect changes the calculated values of γ, which suggests that the model potential parameters should be redetermined. The vibrational dependence of coefficients ξ is analyzed, and they are compared to coefficients ξ calculated for the same lines of the ammonia molecule pressure broadened by H₂, O₂, N₂, and NH₃.     

Plasma resonance in granular silver films deposited on rough surfaces of NaCl and KCl single crystals

Granular silver films deposited on rough NaCl and KCl single-crystal surfaces exhibit, besides the low-frequency plasma-resonance band induced by the light-wave field and the field generated by the grain dipoles, a second, high-frequency plasma-resonance band, which is excited only by the light-wave field at the frequency ω₀ of the natural electron vibrations in the grains. The dielectric constant due to interband transitions was calculated from the known plasma frequency and the dielectric constant of the medium surrounding thegrains, the plasma frequency ω_p of the granular films, and the measured frequency of the maximum of surface plasmon vibrations in solid films. The results obtained agree with the data quoted by other authors.