Excitation of inner-shell states of CO2, COS,CS2, N2O and C2H2 by low energy electron impact

The design of an electron impact spectrometer for use in the study of inner-shell electric-dipole-forbidden transitions is described. The use of the spectrometer to investigate spin-forbidden transitions to inner-shell excited states of CO₂, COS, CS₂, N₂O and C₂H₂ is reported. For all these molecules, excitation of inner-shell triplet states has been observed.     

H2S和H2S+的振动光谱和电子能谱计算

本文基于MOLPRO软件包使用从头算方法计算了星际分子H₂S及其阳离子H₂S⁺的势能面及光电子能谱.首先,在(U)CCSD/cc-pVQZ理论水平下获取了H₂S沿法线坐标展开的势能面,势能面直观描述了不同振动模式耦合对分子能量变化的影响,S-H键的非对称伸缩振动和面内弯曲振动共同作用使得系统势能变化范围明显变大.振动多组态相互作用方法被用来计算非谐振动频率和振动光谱,计算结果显示,倍频和组合频之间出现了强烈的费米共振,使得相应波段处的红外强度显著增强.最后,使用拉曼波函数和收缩不变Krylov子空间方法首次计算了H₂SΧ¹A₁→H₂S⁺ X²B₁的光电子能谱.此项研究有助于进一步理解星际分子的内部结构,并为实验研究及星际观测提供参考.     

Molecular photoelectron spectroscopy at 132.3 eV: N2, CO,C2H4 and O2

The molecular photoelectron spectra of gaseous N₂, CO, C₂H₄ and O₂ were obtained using yttrium Mζ X-rays (132.3 eV). Comparison with spectra taken with MgKα₁₂ X-rays (1253.6 eV) showed the molecular orbitals derived from atomic 2p orbitals to be emphasized in the YMζ spectra. Orbital compositions were confirmed in N₂ and CO, and the presence of several peaks was either better established or detected for the first time (e.g., a ²Π_u state at 23.5 eV in O₂⁺) in C₂H₄ and O₂. The relative cross-section predictions of Rabalais et al. were tested by these spectra. The theoretical values, which were based on ground-state wavefunctions and plane-wave (PW) or OPW continuum states, were found to agree qualitatively with experiment, establishing that this level of theory has diagnostic value. Quantitative agreement is lacking, however. The potential application of 132.3 eV X-rays to the study of photoemission from adsorbed molecules on surfaces is emphasized.     

Simultaneous determination of the ground level abundances of N2O,CO2, CO and H2O

The AFCRL atmospheric line-parameter listing has been used with a non-linear, least-squares method of analysis to obtain the abundances of N₂O and CO in a sample of ground level air with a precision of about 1%. Absorption coefficients calculated for N₂O agree satisfactory with laboratory measurements but an error of 0.0267 cm^-1 in the listed position of an H₂O line at 2205.250 cm^-1 has been corrected and errors in the positions and intensities of CO₂ lines between 2230 and 2250 cm^-1 have been observed.     

Determination of H2S,COS, CS2 and SO2 by an aluminium nitride nanocluster: DFT studies

ABSTRACT

Density functional theory calculations were used to investigate the potential application of an AlN nanocluster in the detection of H₂S, COS, CS₂ and SO₂ gases. In overall, the order of strength of interaction of these gases with the nanocluster is as follows: SO₂ (E_ad?=??17.6?kcal/mol)?>?H₂S (E_ad?=??14.0?kcal/mol)?>?COS (E_ad?=??8.4?kcal/mol)?>?CS₂ (E_ad?=??4.5?kcal/mol). This indicates that by increasing the electric dipole moment, the adsorption energy becomes more negative. We found that the Al₁₂N₁₂ nanocluster may be a promising work function-type sensor for SO₂ gas among the studied gases. Also, it is an electronic sensor for both SO₂ and CS₂ gases but selectively acts between them because of their different effects on the electrical conductivity. It is neither work function-type nor electronic sensor for H₂S and COS gases. The AlN nanocluster benefits from a short recovery time about 7.7?s and 18.0?ms for desorption of SO₂ and CS₂ gases from its surface at room temperature, respectively. It is also concluded that this cluster can work at a humid environment.     

A new force field for the adsorption of H2, O2, N2, CO,H2O,and H2S gases on alkali doped carbon nanotubes

The main goal of this work is the generation of a new force field data set to the interaction of several gases such as H₂, O₂, N₂, CO, H₂O, and H₂S with alkali cation-doped carbon nanotubes (CNTs) using ab initio calculations at the MP2(full)/6-311++G(d,p) level of theory. Different alkali cations including Li⁺, Na⁺_, K⁺ and Cs⁺ were used to dope in the CNT. The calculated potential energy curve for the interaction of each gas molecule with each alkali cation-doped CNTs was fitted to an analytical potential function to obtain the parameters of the potential function. A modified Morse potential function was selected for the fitting in which the electrostatic interactions has been accounted by adding the β/r term to the Morse potential. The accuracy of the calculated force field was checked via Grand Canonical Monte Carlo (GCMC) simulation of the H₂ adsorption on Li-doped graphite and Li-doped CNT. The results of these simulations were compared with the experimental measurements and the closeness of the simulation results with the experimental data indicated the accuracy of the proposed force field. The main merit of this work is the derivation of a specific force field for interaction of each of six gases with four alkali cation-doped CNT, which can be used in molecular simulation of these 24 of systems. The simulation results showed the increase of the H₂ adsorption capacity of nanotube and graphite up to 50% and 10%, respectively, due to the insertion of Li ions.     

Satellite structure in the photoelectron spectra of the core electrons of NO,N2O and H2O

Satellite structures have been observed in the photoelectron spectra of the core shells of nitric oxide, nitrous oxide and water. An attempt has been made to characterize the satellite structure in terms of monopole transitions resulting from electron shake-up. For this purpose comparisons of the observed excitation energies were made with optical data for both (1) the neutral molecules and (2) the analogous equivalent-core molecular ions. Using these energy comparisons and population densities for various molecular orbitals some assignments are made of the orbitals involved in electron shake-up as a function of the core vacancy.     

Real-gas properties of n-alkanes, O2, N2, H2O, CO, CO2, and H2 for diesel engine operation conditions

The objective of the research outlined in this paper was to develop the analytical approximations for calculating real-gas properties (p-v-T data, thermodynamic functions: internal energy, enthalpy, and entropy, and specific heats) of vapor-phase n-alkanes from C₁ (methane) to C₁₄ (normal tetradecane), O₂, N₂, H₂O, CO, CO₂, and H₂ within the range of pressure 0.05 MPa ≤ p ≤ 20 MPa and temperature 280 K ≤ T ≤ 3000 K aimed for implementation into computational fluid dynamics (CFD)-codes simulating the operation process in modern Diesel engines. The analytical approximations have been developed based on available literature data and on the new equation of state for moderately dense gases. The approximations reported are rather simple and therefore can be used directly in CFD codes. Approximations for mixing rules are also provided.     

气相中2Ca＋介入N2O与CO, N2O与H2反应的计算研究

本文采用密度泛函理论DFT-UB3LYP方法, 在6-311+G(2d, p)的基组下, 计算研究了气相中Ca+离子介入N2O (1∑+)和CO (1∑+) 与N2O (1∑+) 和 H2 (1∑+g)反应的微观机理. 报道了二重态势能面上各反应物、中间体和过渡态的构型特征及能量, 并用频率分析和内禀反应坐标（IRC）方法对过渡态进行了验证. 计算结果表明,金属离子参与N2O和CO与N2O和H2的反应都分两步进行, 其中Ca+离子对反应N2O (X1∑+) + CO (1∑+)生成N2 (X1∑+g) + CO2 (1∑+g)比较Fe+, Ir+, Pt+等的金属离子有良好的催化作用, 而对反应N2O (X1∑+) + H2 (1∑+g) → N2 (1∑+g) + H2O (1A1) 催化作用不是很好,N2、CaOH+和H是该反应的主要产物,与实验观测结果相符, 并通过对金属离子亲氧性（OA）的计算, 从热力学方面进一步说明主题反应的可行性.     

气相中2Ca＋介入N2O与CO, N2O与H2反应的计算研究

本文采用密度泛函理论DFT-UB3LYP方法, 在6-311+G(2d, p)的基组下, 计算研究了气相中Ca+离子介入N2O (1∑+)和CO (1∑+) 与N2O (1∑+) 和 H2 (1∑+g)反应的微观机理. 报道了二重态势能面上各反应物、中间体和过渡态的构型特征及能量, 并用频率分析和内禀反应坐标（IRC）方法对过渡态进行了验证. 计算结果表明,金属离子参与N2O和CO与N2O和H2的反应都分两步进行, 其中Ca+离子对反应N2O (X1∑+) + CO (1∑+)生成N2 (X1∑+g) + CO2 (1∑+g)比较Fe+, Ir+, Pt+等的金属离子有良好的催化作用, 而对反应N2O (X1∑+) + H2 (1∑+g) → N2 (1∑+g) + H2O (1A1) 催化作用不是很好,N2、CaOH+和H是该反应的主要产物,与实验观测结果相符, 并通过对金属离子亲氧性（OA）的计算, 从热力学方面进一步说明主题反应的可行性.     

Vibrationally inelastic scattering of H∼ ions from H2, N2, O2 and CO2

State-resolved measurements are presented for vibrational excitation of H₂, N₂, O₂ and CO₂ by H^? impact in the collision energy rangeE _cm=20–180 eV and for scattering in the forward direction (0±0.5°). The data obtained from the measurements are the relative intensities and differential cross sections for vibrational excitation up toν′=4, the transition probabilitiesP _0→ν′ and the vibrational energy transferΔE _vib. For the systems H^?-H₂, N₂, O₂ the vibrational inelasticity increases in the order H₂-N₂-O₂. The mechanism for vibrational excitation in these systems is due to transient charge transfer from the H^? ion into antibonding orbitals of the target molecule which provides a bond stretching force during the collision. For H₂ and N₂, the results are compared with corresponding measurements for H⁺ scattering where the interaction mechanism is quite different. In the case of CO₂, vibrational excitation in forward scattering is caused primarily by the long-range dipole interaction. The spectra are very similar for H^?-CO₂ and H⁺-CO₂. Finer details are attributed to the influence of transient charge transfer and valence interactions.     

UV absorption cross section of the molecules O2, NO,N2O,CO2, H2O,and NO2

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 52, No. 3, pp. 455–465, March, 1990.     

Further study of continuous-wave CO flame chemical laser of the CS2/O2/N2O type

This report describes an experimental examination of the output characteristics of the continuous-wave (cw) carbon monoxide flame chemical laser (FCL) of the CS₂/O₂/N₂O type in case of small CS₂/O₂ reactants ratios (tipically CS₂/O₂≦1/10). A linear burner which gives a homogeneous and stable flame was used during the experimental study. The measurements of temperature distribution in CS₂/O₂ as well as CS₂/O₂/N₂O flames show maximum temperatures of 1040 and 890 K, respectively. The addition of nitrous oxide (N₂O) leads to dramatically enhanced output laser power caused primarily by V?V transfer processes. A chemical efficiency, based on the reaction O+CS→CO^*+S, of 3% was achieved. The spectral composition of the CO FCL of the CS₂/O₂/N₂O type shows lasing in the region from 5.130 to 5.586 μm. Experimental results were obtained with a nondispersive optical cavity.     

Ionization energies of the N2, CO,CO2, N2O,C2H2 and SiH4 molecules calculated by universal model potential

Acta physica Academiae Scientiarum Hungaricae - A modified XαSW method with universal potential (MXαSWU) was used to calculate ionization energies of the N2, CO, CO2, N2O, C2H2 and SiH4...     

The adsorption of CO,O2, and H2 on Pt: II. Ultraviolet photoelectron spectroscopy studies

Ultraviolet photoelectron spectroscopy (UPS) has been used to study the chemisorption of CO, O₂, and H₂ on platinum. Three single crystal surfaces ((111), 6(111) × (100), and 6(111) × (111)) and two polycrystalline surfaces were studied. These studies yielded three important results. First, the most dominant change in the Pt valence band upon gas adsorption was a decrease in the height of the peak immediately below the Fermi level. This decrease was nearly identical for all three gases studied. Second, CO adsorption resulted in the formation of a resonance state ～8 eV below the Fermi level which was attributed to CO molecular orbitals. In contrast, no dominant resonance states were observed for adsorbed O or H. The lack of an O resonance state on platinum is in contrast to the results observed for O adsorbed on Fe and Ni and suggests important differences between the OPt chemisorption bond and the OFe and ONi chemisorption bonds. Finally, adsorption of CO at steps or defects led to a decrease in work function while its adsorption on terraces led to an increase in work function. For H, adsorption at steps led to an increase in work function while adsorption on terraces led to a decrease in work function. The adsorption of O led to an increase in work function on all of the surfaces studied.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

On the additivity of atomic and molecular dipole properties and dispersion energies using H,N, O,H2, N2, O2, NO,N2O,NH3 and H2O as models

The zeroth-order theory of intermolecular forces is used to derive additivity relations for rotationally averaged molecular dipole properties and dispersion energy constants by assuming that a molecule is comprised of non-interacting atoms or molecules. Some of the additivity rules are new and others, for example the mixture rule for dipole oscillator strength distributions (DOSDs), Bragg's rule for stopping cross sections and Landolt's rule for molecular refractivities, are well known. The additivity rules are tested by using previously constructed DOSDs and reliable values for the dipole oscillator strength sums S_k , L_k and I_k , and dispersion energy constants C ₆, for H, N, O, H₂, N₂, O₂, NO, N₂O, NH₃ and H₂O as models. It is found that additivity is generally unreliable for estimating molecular properties corresponding to k < -2. Generally for k ≥ -2 and for C ₆, and if the hydrogen molecule is used to represent the hydrogen atom in the additivity rules, the additivity relations yield results that are reliable to within ?20 per cent and the estimates improve substantially as k increases. The effects of molecule formation on DOSDs is examined by comparing the various molecular DOSDs with the sum of the DOSDs for the atoms making up the molecules. Molecule formation results in a net decrease in the amount of dipole oscillator strength for low excitation energies and a compensating net increase for higher energies in a region extending from the absorption threshold to about 100 eV. This is shown to imply that estimates of the stopping average energy I ₀, obtained by using bona fide atomic I ₀ values, are lower bounds to the correct molecular I ₀ results.     

Photoionization and photoelectron angular distribution for H2

Photoionization of H₂(¹Σ_g⁺) in a vibrational υ″ and rotational N″ state into H₂⁺(²Σ_g⁺) in a vibrational υ′ and rotational N′ state is studied theoretically. The differential cross section, after summing over the final states, is expressed in the well-known simple form of $\text{(}\text{σ}{}_{\mathrm{T}}\text{4π}\text{)[1 + βP}{}_2\text{(}\text{cos}\text{θ)]}$. Parallel expressions are obtained for H₂⁺ in a specific υ′ state (in terms of σ(υ′) and β(υ′)) and for H₂⁺ in a rotational fine level υ′N′ (in terms of σ(υ′N′) and β(υ′N′)). Asymmetry parameters β, β(υ′) and β υ′N′), which are expressed in terms of Racah and Clebsch-Gordan coefficients and electronic transition moments, can be reduced approximately to 2 lineary polarized light and to -1 for unpolarized light. Using single-center electronic wave functions and including partial eaves l = 1, 3, and 5, σ(υ′) and β(υ′) are computed as a function of υ′ at 584 Å. The computed σ(υ′) divided by the Frank-Condon overlap, in agreement with experimental results, increases monotonically with υ′; σ_T and β are computed in the incident photon energy range of 600–4000 Å and the results compare favorably with previous calculations.     

FTIR-spectra of solid O2, N2 and CO

FTIR measurements of thin films of N₂, O₂ and CO at about 20 K contain a line due to the allowed or induced fundamental transition and a broad structure shifted to higher frequencies. This phonon sideband is explainable by coupling of lattice vibrations to the molecular fundamental vibration, and mirrors the weighted one phonon density-of-states. This IR-derived density-of-states can be compared with those from other experimental studies (neutron scattering, Raman) and from theoretical models.