Effect of Excitation and Vibrational Temperature on the Dissociation of Nitrogen Molecules in Ar-N2 Mixture RF Discharge

Non-equilibrium argon-nitrogen mixture plasma generated at 13.56 MHz is characterized by optical emission spectroscopy and Langmuir probe techniques. The excitation and vibrational temperature are studied as a function of argon percentage in the mixture, at 30-Pa filling pressure and input RF powers of 200 and 300 watt, to find out their role in dissociation of N₂ molecules. In this work, the excitation temperature is determined from Ar-I emission line intensities by using the simple Boltzmann plot method and is found to increase with argon mixing in nitrogen plasma. In similar fashion, the vibrational temperature of second positive system has been determined and is found to also have increasing trend with argon addition. The effect of excitation and vibrational temperature on the nitrogen molecular dissociation level is also monitored. It is observed that N/N ₂ ratio increases with increase in excitation and vibrational temperature and falls slightly at the end.     

Electron spectroscopy of autoionizing states of nitrogen atoms

During excitation of N₂, NO and N₂O molecules by fast neutral 1¹S helium atoms, highly excited molecular states are formed which yield, through predissociation, autoionizing nitrogen atoms. The energy of electrons released in autoionization was measured and the energy and plausible spectroscopic assignment of autoionizing levels was determined. The excited levels belong to Rydberg series converging to the N⁺(¹D) series limit. Besides molecular states derived by correlation of the final atoms, highly excited molecular parent states are also discussed.     

Mikrophysikalische Bestimmung elektronenkinetischer Kenngrößen im binären Molekül-Mischplasma von Stickstoff und Wasserstoff. II. Elektronenstoßfrequenzen für die Anregung und Ionisierung langlebiger elektronischer Molekülzustände und die Energieverlustraten der Elektronenkomponente des Mischplasmas

In this second part of the in [l] started paper the results of microphysical determined collision frequencies of the electrons for the excitation and ionization of metastable molecules, excited in electronic states, and of the energy loss rates of the electrons due to elastic collisions, vibrational excitation, electronic excitation, dissociation and ionization of the molecules in a N₂ - H₂ -plasma are represented and discussed. These investigations are related to a low ionized, homogeneous and stationary plasma in a mixture and are performed for the range 6- 100 V/(cm Torr) of the reduced electric field strength and for any composition of the N₂ - H₂-mixture.     

Modeling of synthesis and dissociation of the N<Subscript>4</Subscript> nitrogen cluster of D<Subscript>2H</Subscript> symmetry

Within the framework of multi-configurational self-consistent field (MCSCF) approximation, the ground and excited states of the N₄(D_2H) cluster of N₂ molecules are modeled from different initial states. The potential barriers to the cluster formation and dissociation are calculated. Investigations of the N₄(D_2H) electronic spectrum demonstrate that the most promising method of forming nitrogen nanostructures is compression of the excited triplet N₂ molecules.     

Optical emission spectroscopy of 50 Hz pulsed dc nitrogen–hydrogen plasma in the presence of active screen cage

The N₂-H₂ plasma gas mixture, generated in a 50?Hz pulsed dc discharge system with active screen cage, is characterized by optical emission spectroscopy (OES), as a function of gas pressure, the fractions of hydrogen and current density. The N₂ dissociation degree and N atomic density was measured with actinometery where argon gas is used as actinometer. It was shown that the increase in hydrogen fraction enhances the dissociation of N₂, until the maximum of 40%. The excitation temperature is determined from Ar-I emission line intensities by using the simple Boltzmann plot method. The dissociation fraction and excitation temperature is found to increase with hydrogen mixing in nitrogen plasma.     

Kinetic parameters,collision rates,energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO₂ and N₂ as well as impact dissociation of O₂ being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 10¹⁰ cm^?3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed.     

Radiative Transitions and Temperature Time Dependences in Pulse Excited Microwave Discharges – (N2, Ar + N2)

Quantitative spectral and microwave measurements of vibrational temperatures and electron densities were performed for 2400 MHz non-isothermic pulse excited discharges in flowing nitrogen and argon at pressures (60–2700) Pa. A detailed analysis of the N₂ vibrational states population for the N₂ C³Π_u, X¹Σ_g⁺ electronic states has been carried out. The basic difficulties encountered when comparing the spectroscopically determined values of vibrational temperatures with corresponding quantities of the ground electronics state are mentioned and the time resolved dependences of the translational gas temperature in N₂ during the microwave pulse is evaluated. The steady state in the nitrogen pulse excited microwave plasma is reached within 3 · 10^?4 s, but generally, this time depends on the gas pressure in the discharge tube. In the Ar + N₂ mixtures the excitation conditions are complicated by the metastable argon atoms (3P_2,0) creating the nonequilibrium populations of electronic, vibrational and rotational N₂ states.     

Spectroscopical Observation of a Relaxing High Speed Nitrogen Plasma Jet

A near sonic nitrogen plasma jet operating at pressures between 100 Torr and 1 atm has been investigated spectroscopically. From the absolute emission coefficient of a NI spectral line, local values for the electron temperature T_e have been derived. For pressures above 200 Torr, T_g was found to coincide within the limits of experimental error with the gas temperature T_g. The latter quantity has been determined via the relative emission coefficient of selected rotational line components of the N₂⁺ molecular band at 3914 Å. The results of these measurements together with control data for the electron density derived from the continuous emission coefficient indicate that at pressures above 200 Torr the existence of a thermal equilibrium between the degrees of freedom corresponding to particle translation, electron excitation, and ionization can be accepted, at least for the inner zone of the plasma jet. To the contrary, the data for the absolute emission coefficient of N₂⁺ molecular band lines show that the degree of dissociation in the plasma jet is much in excess of that corresponding to equilibrium. This phenomenon can be explained as a result of the rapid temperature decay in the plasma from initially 13000 K in the arc heating zone to T ≦ 9000 K in the plasma jet zone proceeding in a time interval of 10^?5 s which is much shorter than the time necessary for adjustment of dissociation equilibrium. In the outer cool zone of the plasma jet, an unusual high intensity of the N₂⁺ radiation was found thus indicating the existence of a nonequilibrium excitation mechanism typical for a decaying nitrogen plasma. From the supernormal high degree of dissociation in the high-speed subatmospheric nitrogen plasma jet, conclusions are drawn with respect to its applicability as source of reactive particles in plasma-chemical experiments.     

Intensity dependence of multiphoton dissociation in formaldehyde

A new intensity-dependent measurement of multiple-photon dissociation (MPD) in H₂CO, HDCO, and D₂CO gases by the use of an intense pulsed CO₂TEA laser is reported. In this measurement the energy and duration of the laser pulses are kept constant, and the intensity is varied by irradiating the sample using concave mirrors of different focal lengths. A model calculation is used to analyze and fit the present and previous experimental MPD data of HDCO and D₂CO. In this model it is assumed that dissociation is obtained by a repeated mechanism in which coherent multiphoton excitation (CME) of the molecule to high vibration-rotation states |v, J〉 is followed by intramolecular transfer of the excitation energy (ITEE) to the other modes of the molecule. In the calculations the CME is described in the framework of the density matrix formalism with relaxations, and is used to calculate absorption from the ground state as well as absorption from excited states reached by the energy redistribution in the molecule. The ITEE process is assumed to be intensity independent and to cause a random energy distribution in each transferring process. It is found that the experimental results are consistent with the absorption of 14±4 and 17±5 photons per molecule for HDCO and D₂CO, respectively, and this is sufficient to cause their dissociation.     

Neutral Dissociation of Superexcited Nitric Oxide Induced by Intense Laser Fields

利用波长800 nm、脉宽60 fs、强度0.2 PW/cm²的强激光激发NO分子,随后通过荧光光谱检测到了处于激发态的N和O的中性碎片. 说明强激光导致的多光子激发同样可以引起NO分子的超激发,并且发生中性解离. 采用离子实解离模型,建立了NO分子的超激发态势能曲线. 提出了直接解离和预解离两种解离过程,分别对应生成N^*+O或O^*+N两个通道.     

Highly accurate excited-state energies from direct computation of the 2-electron reduced density matrix by the anti-Hermitian contracted Schrödinger equation

ABSTRACT

Directly solving for the 2-electron reduced density matrix (2-RDM) via the anti-Hermitian contracted Schrödinger equation (ACSE) enables computations for excited states energies without the N-electron wave function. Of particular interest are excitations and dissociation curves that exhibit strong multi-reference correlation effects. The ground and excited states of the molecules HF, H₂O, and N₂ are examined at both equilibrium and non-equilibrium geometries to compare the ability of the ACSE and widely used ab initio techniques to treat strong multi-reference electron correlation. Calculations are performed with double-ζ basis sets for calibration with full configuration interaction (FCI). Multi-reference second-order perturbation theory (MRPT2) and the ACSE both provide qualitative precision with respect to FCI data, although the ACSE's capability to include higher order correlation effects permits near-FCI accuracy for ground and excited states and excitation energies.     

NO excitation and thermal non-equilibrium within a flat plate boundary layer in an air plasma

Optical emission spectroscopy experiments are carried out by recording the radiation from the γ transitions of nitrogen monoxide in an air inductively coupled plasma in interaction with a water-cooled metallic flat plate at moderate pressure. The calibrated results allow to derive the vibrational and rotational temperatures of the NO(A ² Σ ⁺) excited state as well as its densities in the free jet and within the boundary layer by comparison with calculated spectra. Those results are compared with previous ones concerning temperatures and densities of the ground states of the majority species (N₂, O₂ and NO) that were obtained by laser techniques. As for the NO(X ² Π) ground state, vibration and rotation of the excited state are found out of equilibrium. The NO(A ² Σ ⁺) excited state is found to be populated by an energy transfer from the metastable N₂( A³\varSigma ⁺_uA^{3}\varSigma ^{+}_{u}). The steady state of the plasma allows using this property to derive N₂( A³\varSigma ⁺_uA^{3}\varSigma ^{+}_{u}) densities and N₂ electronic excitation temperatures. Close to the wall, a production of excited NO by a catalytic process is also considered involving N₂( A³\varSigma ⁺_uA^{3}\varSigma ^{+}_{u}) as source of adsorbed atoms. The present results confirm that the kinetic temperature cannot be compared to the rotational temperature derived from optical emission spectroscopy in such plasma conditions.     

Excitation,inversion, and relaxation mechanisms of the HCN FIR discharge laser

Millimeter/submillimeter rotational absorption spectroscopy has been used as a diagnostic probe of a cw HCN discharge laser. This sensitive technique allowed in situ absolute population measurements of a number of vibrational states of HCN (including the upper lasing state) and other pertinent molecules. This unique set of data, which was obtained under a variety of discharge and laser conditions, is directly related to excitation, inversion, and relaxation processes. Along with elucidating several fundamental aspects of inversion and relaxation these results also strongly indicate that the primary laser excitation mechanism is near-resonant energy transfer from vibrationally excited nitrogen, N₂ (v=1), to the fundamental symmetric stretching mode of hydrogen cyanide, HCN(100), and subsequent thermal population exchange between HCN (100) and the upper laser state, HCN (110).Work supported by ARO Contract DAAG-29-83-K-0078     

Effect of molecular nitrogen on the electron mobility in a mixture of argon and optically excited sodium vapor

A parametric study of the electron energy distribution function (EEDF) and the electron mobility in the mixture Na + Ar + N₂ is carried out. An analysis is made of the conditions that obtain in a photoplasma when the detachment of the mean electron energy from the neutral gas temperature is due to superelastic collisions (collisions of the second kind) with excited sodium atoms. The case of low ionization of the medium at low vibrational temperatures of the ground state of the nitrogen molecules is considered. To find the EEDF a numerical solution of the Boltzmann transport equation is carried out. It is found that in the indicated mixture the presence of nitrogen leads to a depletion of the EEDF in the region of efficient vibrational excitation of the molecules and promotes the formation of inversion in the EEDF ∂f(ɛ)/∂ɛ>0 in the energy range corresponding to the Ramsauer minimum in the cross section of elastic collisions of electrons with the argon atoms. It is shown that the nonequilibrium character of the EEDF leads to a complicated dependence of the electron mobility on the partial ratios of the components of the mixture, the degree of ionization of the medium, and the population of the resonantly excited sodium atoms. Zh. Tekh. Fiz. 69, 14–19 (April 1999)     

振动和转动激发对N2在Fe(111)表面解离吸附的影响

N₂的解离化学吸附是工业合成氨的速控步骤. 基于最近构建的六维势能面,本文研究了N₂的初始振动激发和转动激发在Fe(111)表面的反应性的作用. 由于该反应具有重要的量子效应,通过六维量子动力学计算研究了入射能量低于1.6 eV 时振动激发的效应. 并采用准经典轨线计算揭示了高入射能量下的振动和转动激发的影响. 通过这些研究发现增加平动能量在一定程度上能提高解离几率,振动激发或转动激发能更有效地促进解离. 这项研究为重原子分子-表面反应的模式特异性动力学提供了有价值的见解.     

High-resolution,near-infrared CW-CRDS,and ab initio investigations of N2O–HDO

We have investigated the N₂O–HDO molecular complex using ab initio calculations at the CCSD(T)-F12a/aug-cc-pVTZ level of theory and using cavity ring-down spectroscopy to probe an HDO/N₂O/Ar supersonic jet around 1.58 μm. A single a-type vibrational band was observed, 13 cm^?1 redshifted compared to the OH+OD excited band in HDO, and 173 vibration-rotation lines were assigned (T_rot ≈ 20 K). A weighted fit of existing microwave and present near infrared (NIR) data was achieved using a standard Watson's Hamiltonian (σ = 1.26), producing ground and excited states rotational constants. The comparison of the former with those calculated ab initio suggests a planar geometry in which the OD rather than the OH bond in water is almost parallel to NNO. The equilibrium geometry and dissociation energy (D_e = –11.7 kJ/mol) of the water–nitrous oxide complex were calculated. The calculations further demonstrate and allow characterising another minimum, 404 cm^?1 (ΔE₀) higher in energy. Harmonic vibrational frequencies and dissociation energies, D₀, were calculated for various conformers and isotopic forms of the complex, in both minima. The absence of N₂O–D₂O from dedicated NIR experiments is reported and discussed.     

甲醛的态选择性多光子电离研究

我们在XeCl准分子激光多光子电离甲醛分子的研究中,获得了甲醛经过2+1和2+2光子共振激发过程而产生的母体离子和高能离解通道的离子CO⁺。在电子轰击和单光子电离中占优势的低能阈离解通道离子HCO⁺,由于态选择性激发的结果而未出现。 关键词：     

Ultrafast dynamics in the excited hydrogen atom transfer states of ammonia clusters

Neutral ammonia clusters (NH₃)_m are photo-excited to the electronic state by a deep UV femtosecond laser pump pulse. Within a few hundred femtoseconds a significant fraction of the clusters rearrange to form an H-transfer state (NH₃)_m-2NH₄(3s)NH₂ with the subunit NH₄ in its 3s electronic ground state. This state is then electronically excited by a time-delayed infrared control pulse of variable wavelength. Finally, a third (probe) pulse in the UV ionizes the clusters for detection. The lifetime of the excited (NH₃)_m-2NH₄(3p)NH₂ states is found to vary between 2.7 and 0.13 ps depending on cluster size and excitation energy. It increases drastically upon deuteration. The corresponding cluster size-dependent photoelectron spectra allow us to disentangle the underlying energetics of the excitation and ionization process and reveal additional processes, such as nonresonant ionization or dissociative ionization. The experimental findings suggest that the excited H-transfer ammonia complexes with m > 2 are deactivated by an internal conversion process back to the electronically lowest H-transfer state followed by fast dissociation. Received 22 September 2001 and Received in final form 31 January 2002     

Enhanced dissociation of H2+ into highly excited states by UV pulses

We theoretically study the dissociation of H₂⁺ by UV laser pulses as a function of the photon energy ω of the pulse. Our results show that pronounced enhancements of the dissociation into highly excited electronic states can be achieved at some critical ω. This is found to be attributed to a consecutively resonant excitation mechanism where the population is first transferred to the first excited state by absorbing one photon and then to higher states by absorbing another one or more photons at the same internuclear distance. This study indicates that the strong coupling between the lowest two states of H₂⁺ can significantly affect the dissociation through higher lying states.     

A quasiclassical study of collisions of He with HD(B 1Σ+ u )

A quasiclassical trajectory study has been carried out for collisions of ⁴He with electronically excited H₂(B ¹Σ⁺ _u ) and its isotopomer HD. By using analytical fits for the ab initio potential energy surfaces of the ground and the excited state we have obtained vibrational and electronic quenching cross sections for several initial conditions. We draw the following conclusions. Vibrational excitation strongly promotes electronic quenching whereas translational energy is less effective. Rotational excitation decreases the rate of quenching. In a remarkable contrast to the ground electronic state, vibrational energy transfer on the excited potential energy surface is an efficient and fast process. Collisions at high energies results in T → R energy transfer. The above conclusions are valid for both H₂ and HD.