氯与甲烷和重氢甲烷反应的矢量相关研究

在扩展的London-Eyring-Polanyi-Sato(LEPS)势能面基础上,利用准经典轨线法在碰撞能Ecol=3.67 kcal/mol下研究了Cl+CH4→HCl+CH3和Cl+CD4→DCl+CD3反应,在质心系计算得到四个广义极化微分反应截面((PDDCS)(2π/σ)(dσ00/dωt)、(2π/σ)(dσ20/dωt)、(2π/σ)(dσ22+/dωt)、(2π/σ)(dσ21-/dωt)和k-k′-j′三矢量相关的极角分布p(фr)、k-j′两矢量相关的p(θr)分布以及用θr和фr表示的产物转动角动量的空间分布.计算结果与有关实验及理论结果符合得很好,讨论了氯与甲烷和重氢甲烷反应的立体动力学同位素效应.     

Ca+CH_3I→CaI+CH_3反应的矢量相关研究(英文)

本文采用准经典轨线方法,在LEPS势基础上计算了Ca+CH3I→CaI+CH3在不同碰撞能下的矢量相关计算了质心系中四个广义极化微分反应截面(2π/σ)(dσ00/dωt),(2π/σ)(dσ20/dωt),(2π/σ)(dσ22+/dωt),(2π/σ)(dσ21-/dωt),k-j′两矢量相关的P(θr)分布、k-k′-j′三矢量相关的极角分布P(φr)以及用θr和φr表示的产物转动角动量的空间分布P(θr,φr).     

氯与甲烷和重氢甲烷反应的矢量相关研究

在扩展的London Eyring Polanyi Sato（LEPS）势能面基础上，利用准经典轨践法在碰撞能Ecd=3．67 kcal／mol下研究了Cl＋CH4→HCl＋CH3和Cl＋CD4→DCl＋CD3反应，在质心系计算得到四个广义极化微分反应截面（（PDDCS）（2π／σ）（dσ00／dωt）、（2π／σ）（dσ20/dωt）、（2π／σ）（dσ22／dωt）、（2π／σ）（dσ21／dωt）和k—k’- j’三矢量相关的极角分布P（φr）、k—j’两矢量相关的P（θr）分布以及用以和丸表示的产物转动角动量的空间分布．计算结果与有关实验反理论结果符合得很好，讨论了氯与甲烷和重氢甲烷反应的立体动力学同位素效应。     

同位素对Ca+HCl，Ca+DCl，Ca+TCl反应立体动力学性质的影响

基于准经典轨线方法和Verbockhaven等人通过多参考组态相互作用计算建立的势能面研究了Ca+HCl/Ca+DCl/Ca+TCl反应中的矢量相关效应. 计算和分析了 P(θr)和 P(Φr)以及(2π/σ)(dσ₀₀/dω_t), (2π/σ)(dσ₂₀/dω_t), (2π/σ)(dσ₂₂₊/dω_t), (2π/σ)(dσ_21-/dω_{t相似文献}   

Cl与C3D6H2和C3H6D2反应的立体动力学对比研究

在扩展的London-Eyring-Polanyi-Sato(LEPS)势能面上,利用准经典轨线法研究了碰撞能为Ecol=6.0 kcal/mol时Cl与C3D6H2和C3H6D2反应.在质心系中计算了极化微分反应截面(2π/σ)(dσ00/dtω)、两矢量相关的P(rθ)分布、三矢量相关的极角分布P(Φr)以及用θr和r表示的产物转动角动量的空间分布,计算结果与有关实验及理论结果符合得很好.通过对比研究Cl与C3D6H2、C3H6D2和C3H8在不同碳位上的反应,发现质量因子在此类反应中起着重要的作用.     

Theoretical study of stereodynamics for the D'+ DS(v=0,j=0) → D'D + S abstraction reaction

Quasiclassical trajectory (QCT) calculations have been performed for the abstraction reaction, D'+ DS(v = 0, j = 0) → D'D + S on a new LZHH potential energy surface (PES) of the adiabatic 3 A electronic state [Lü et al. 2012 J. Chem. Phys. 136 094308]. The collision energy effect on the integral cross section and product polarization are studied over a wide collision energy range from 0.1 to 2.0 eV. The cross sections calculated by the QCT procedure are in good accordance with previous quantum wave packet results. The three angular distribution functions, P(θr), P(φr), and P(θr,φr), together with the four commonly used polarization-dependent differential cross sections ((2π/σ)(dσ00/dωt), (2π/σ)(dσ20/dωt), (2π/σ)(dσ22+/dωt), (2π/σ)(dσ21/dωt)) are obtained to gain insight into the chemical stereodynamics of the title reaction. Influences of the collision energy on the product polarization are exhibited and discussed.     

Theoretical study of the stereodynamics of the He＋HD^＋ reaction

This paper investigates the stereodynamics of the reaction He+HD+ by the quasi-classical trajectory(QCT) method using the most accurate AQUILANTI surface [Aquilanti et al 2000 Mol.Phys.98 1835].The distribution P(φr) of dihedral angle and the distribution P(θr) of angle between k and j have been presented at three different collision energies.Four generalized polarization-dependent differential cross-sections(2π/σ)(dσ00/dωt),(2π/σ)(dσ20/dωt),(2π/σ)(dσ22+/dωt),(2π/σ)(dσ21 /dωt) are also calculated.Some interesting results are obtained from the comparison of the stereodynamics of the title reaction at different collision energies.     

Quasi-classical trajectory study of collision energy effect on the stereodynamics of H + Br O → O + HBr reaction

Quasi-classical trajectory(QCT) studies on the stereodynamics of H + Br O → O + HBr reaction have been performed on the X1A′state of ab initio potential energy surface by Peterson [Peterson K A 2000 J. Chem. Phys. 113 4598] in a collision energy range from 0 kcal/mol to 6 kcal/mol. Two of the polarization-dependent generalized differential cross sections(PDDCSs),(2π /σ)( dσ00/ dωt)(PDDCS00) and(2π /σ)( dσ20/ dωt)(PDDCS20) are considered. The rotational polarizations of these products show sensitive behaviors to the calculated collision energy range. Furthermore, in order to gain more knowledge about vector correlations, the product angular distribution, P(θr), and the dihedral angle, P(φr),are calculated, and the results indicate that both the rotational alignment and orientation of the product are enhanced as collision energy increases.     

C1与C3D6H2和C3H6D2反应的立体动力学对比研究

在扩展的London-Eyring-Polanyi-Sato（LEPS）势能面上，利用准经典轨线法研究了碰撞能为Ecol=6．0kcal／mol时C1与C3D6H2和C3H6D2反应．在质心系中计算了极化微分反应截（2π／σ）（dσ00／dωt）、两矢量相关的P（θr）分布、三矢量相关的极角分布P（Ф）以及用θr和Фr表示的产物转动角动量的空间分布，计算结果与有关实验及理论结果符合得很好．通过对比研究C1与C3D6H2、C3H6功和C3H8在不同碳位上的反应，发现质量因子在此类反应中起着重要的作用．     

The collision energy effect on the stereodynamics of the Ca + HCl→CaCl + H reaction

The stereodynamics of the reaction of Ca + HCl are calculated at three different collision energies based on the potential energy surface [Verbockhaven G et al. 2005 J. Chem. Phys. 122 204307] using quasi-classical trajectory theory. The polarization-dependent differential cross sections (PDDCSs) (2π/σ )(dσ 00 /dω t ), (2π/σ )(dσ 20 /dωt ), (2π/σ )(dσ 22+ /dωt ), (2π/σ )(dσ 21 /dω t ) and the distributions of P(θ r ), P(φr ), and P(θr ,φr ) are calculated. The results indicate that the rotational polarization of the CaCl product presents different characteristics for the different collision energies, and the effects of the collision energy on the vector potential, including the alignment, orientation, and PDDCSs, are not obvious.     

基于光谱吸收的光纤甲烷监测系统在瓦斯抽采中的应用

研究了一种基于光谱吸收的光纤甲烷远程实时在线监测系统,分析了该系统在瓦斯抽采中的应用.该系统以1665nm波长半导体激光器作为光源,以单片机C8051F410为核心处理器,采用锯齿波信号实现了气体激光吸收光谱的波长调制,结合A/D转换电路、通讯电路和显示电路,可进行声光报警、LCD液晶显示等.利用内置参考池对激光波长漂移进行自适应调整,可以实现甲烷吸收线的锁定.该系统已在国内外建立多个示范工程,试验表明,该系统具有很好的稳定性,在0%～100%量程实现了分布式多点甲烷气体浓度的实时在线监测和显示,监测的灵敏度可达ppm量级,在煤矿瓦斯抽采领域具有广泛的应用前景.     

THz spectrum of monodeuterated methane

We report new measurements of the rotational spectrum of monodeuterated methane (CH₃D) in the range of 690-1200 GHz which allow for an accurate prediction of all lines in the range of the high-resolution spectrometer of the Herschel Space Observatory. Comparison is also made with the previous analysis based on infrared combination differences. Three lines of ¹³CH₃D were measured in natural abundance.     

High-temperature emission spectroscopy of methane

A high-enthalpy source (HES) has been developed in Rennes either to heat gases up to 2000 K in local thermodynamic equilibrium (LTE) or to generate hypersonic expansions. The HES prototype has been associated with a high-resolution Bruker IFS 120 HR Fourier transform spectrometer to record emission spectra of hot gases, in LTE conditions. A series of emission spectra of methane has been obtained at 1005, 1365, 1485, 1625 and 1820 K in the pentad spectral region located around 3000 cm⁻¹, at Doppler-limited resolution (0.02 cm⁻¹). Spectra have been corrected for the transmission function that strongly affects the infrared radiation emitted by the hot gas. Line-integrated absorption cross sections have been extracted from the corrected spectra using an improved procedure for the calculation of the total partition function Q of methane at high temperature. This calculation included anharmonicity and rovibrational interaction effects, and was based on a multi-resolution fully converged direct partition sum. It has been shown that, as the temperature increases above 1000 K, the commonly used harmonic and rigid rotor double approximation to estimate Q leads to underestimated values.     

Rotational partition function of methane

An analytical formula for the quantum-mechanical rotational partition function of tetrahedral XY₄ molecules is shown to be accurate to better than 1% for methane at temperatures T ≥ 40°K.     

Phase behavior of methane haze

Methane aerosols play a fundamental role in the atmospheres of Neptune, Uranus, and Saturn's moon Titan as borne out by the recent Cassini-Huygens mission. Here we present the first study of the phase behavior of free methane aerosol particles combining collisional cooling with rapid-scan infrared spectroscopy in situ. We find fast (within minutes) phase transitions to crystalline states directly after particle formation and characteristic surface effects for nanometer-sized particles. From our results, we conclude that in atmospheric clouds solid methane particles are crystalline.     

Vibrational intensities in methane

The absorption intensities of the two infra-red active vibrations in methane have been obtained from a perturbation calculation on the equilibrium wave functions derived in the preceding paper. The perturbation field is the change in the potential field due to the nuclei which results from moving the nuclei in the vibrational coordinate concerned, and a simplified form of second order perturbation theory, developed by Pople and Schofield, is used for the calculation. The main approximation involved is the neglect of f and higher harmonics in the spherical harmonic expansion of the nuclear field. The resulting dipole moment derivatives are approximately three times larger than the experimental values, but they show qualitative features and sign relationships which are significant.

The experimental intensity measurements are interpreted and discussed in relation to these results.     

Melting curves of argon and methane

The melting curves of argon and of methane have been measured in a diamond-anvil cell from 290 to>700 K. Measurements of argon, fit to the equation P?6.9×10^?5=0.244[(T/83.805)^1.476?1], are in excellent agreement with previously published values up to a temperature of ～ 500 K and thereafter diverge slowly. Measurements of methane, fit to P?1.17×10^?5=0.208[(T/90.6941)^1.698?1], are in serious disagreement with the only previous studies to extend past 400 K.     

Characteristics of microjet methane diffusion flames

Characteristics of microjet methane diffusion flames stabilized on top of the vertically oriented, stainless-steel tubes with an inner diameter ranging from 186 to 778 μ m are investigated experimentally, theoretically and numerically. Of particular interest are the flame shape, flame length and quenching limit, as they may be related to the minimum size and power of the devices in which such flames would be used for future micro-power generation. Experimental measurements of the flame shape, flame length and quenching velocity are compared with theoretical predictions as well as detailed numerical simulations. Comparisons of the theoretical predictions with measured results show that only Roper's model can satisfactorily predict the flame height and quenching velocity of microjet methane flames. Detailed numerical simulations, using skeletal chemical kinetic mechanism, of the flames stabilized at the tip of d = 186, 324 and 529 μ m tubes are performed to investigate the flame structures and the effects of burner materials on the standoff distance near extinction limit. The computed flame shape and flame length for the d = 186 μm flame are in excellent agreement with experimental results. Numerical predictions of the flame structures strongly suggest that the flame burns in a diffusion mode near the extinction limit. The calculated OH mass fraction isopleths indicate that different tube materials have a minor effect on the standoff distance, but influence the quenching gap between the flame and the tube.     

An acoustic estimate of methane concentration in a water column in regions of methane bubble release

A remote acoustic method is presented for estimating the methane flux into water from rising bubbles. With the proposed method and data of hydroacoustic measurements in the Sea of Okhotsk, the dissolved methane concentration profile that forms in the water column in regions of methane bubble release is estimated. Comparison of the aforementioned methane concentration profile with results of direct measurements shows good quantitative and qualitative agreement. This testifies to the fair accuracy of the proposed acoustic method and is indicative of the dominant role of bubble transport in the formation of the concentration of dissolved methane in the water column in such regions.