Linear concentration dependence of vibrational width and vibrational dephasing paths in aqueous nitrate solutions

A theoretical model of vibrational dephasing of Raman active ions in aqueous electrolyte solutions is presented in which a probe ion is coupled to the bath by direct ion-solvent and ion-ion interactions. Expression for the vibrational width in terms of concentrations and efficiencies of the vibrational frequency modulation by ion-perturber interactions is given in the fast modulation scheme. The observed linear concentration dependence of the vibrational dephasing width of the v ₁(A'₁) mode of NO₃ ^- in aqueous solutions is reasonably well explained from this model, and efficiencies of the dephasing paths through NO₃ ^--water hydrogen bonding interaction and contact NO₃ ^--cation pair formation interaction are estimated. Anions in the solution give only a secondary effect to nitrate vibrational dephasing because of interionic repulsive forces.     

Time domain investigation on vibrational dephasing and spectral diffusion in CO-doped solid N2

Infrared picosecond accumulated photon echo experiments have been performed for the first time, using the Orsay Free Electron Laser, on the v = 0-->v = 1 transition of CO in solid nitrogen. The vibrational dephasing time is found to be exceptionally long ( T2>/=120 ns) at low temperature. The analysis of the observed spectral diffusion leads one to assume different energy transfer mechanisms depending on the CO concentration.     

Laser schlieren measurement of vibrational relaxation times for N2O in mixtures containing CO,N2, and Ar behind a shock wave

The laser schlieren method has been used behind shock waves where the temperatures are 410–2400°K to measure the vibrational relaxation times for N₂O and also for mixtures of N₂O with CO, N₂, and Ar. The vibrational relaxational times of N₂O have been measured for collisions with these partners, and it has been found that the effectiveness of N₂ in relaxation is close to that of N₂O, whereas CO results in accelerated vibrational relaxation of N₂O. A comparison is made with the available published data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 3–8, November, 1984.We are indebted to V. V. Savkin for performing the mass spectral analyses.     

Search for anomalous effects in H2O/D2O mixtures by neutron total cross section measurements

We investigate anomalies ascribed to quantum entanglement phenomena recently reported in deep inelastc neutron scattering (DINS) measurements by an independent neutron technique on H(2)O/D(2)O mixtures. We performed transmission experiments to study several liquid H(2)O/D(2)O mixtures at room temperature in the epithermal energy range. We obtain the total cross sections of the mixtures, which are in agreement with the expected results according to the tabulated values within a 0.3% relative error. We observe no anomalies and stress the limitations of the validity of the data-processing procedures employed in the DINS experiments where the anomalies were reported.     

Velocity imaging spectrometer for negative fragment ions: application to dynamics of O2 and N2O ion-pair dissociation

A velocity imaging spectrometer has been developed to observe negative ions from molecular ion-pair dissociation. The imaging spectrometer is equipped with a pair of permanent magnets. The resulting magnetic field prevents efficiently the electrons from reaching the detector, without seriously affecting negative ions’ trajectories. The performance of the imaging spectrometer is demonstrated by the observations of photoelectrons from O₂ and He, and O⁻ from O₂. Application to ion-pair dissociation of O₂ and N₂O is presented, and it proves that the present imaging method provides useful information on the assignments of superexcited states and on the dynamics of ion-pair dissociation.     

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO₂ and N₂O in N₂:O₂:CO₂ and N₂:O₂:CO₂:NO₂ mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm³/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N₂:O₂:CO₂ mixture the corona discharge produced NO, NO₂ and N₂O. In the N₂:O₂:CO₂:NO₂ mixture the reduction of NO₂ was between 6–56%, depending on the concentration of O₂, gas flow rate and corona discharge current. The NO₂ reduction was accompanied by production of NO and N₂O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N₂ and O₂ if reducing additives are not employed.     

Verification of positive streamer mechanism for negative corona Trichel pulses in O2/H2 mixtures

Current waveforms of the first negative corona pulses have been measured in O₂ + H₂ mixtures at a pressure range from 27 kPa to 50 kPa. It was observed that the hydrogen admixtures less than 4% do not change significantly the pulse current waveforms. Effects of changing cathode secondary electron emission were studied using a copper cathode coated by CuI and graphite. The results obtained support the theory of the cathode-directed streamer formation during the negative corona pulse rise.     

Comparison of dephasing times for vibrational and rotational coherent anti-Stokes Raman scattering: implications for velocimetry

Time-domain coherent anti-Stokes Raman scattering experiments have been carried out by probing vibrational and pure rotational lines of nitrogen in the Doppler broadened regime. The theoretical analysis of the transient responses outlines the role of the geometrical effects. For pure rotational CARS, it is shown that the main contribution to the dephasing of the Raman coherence results from the change in direction between the pump and anti-Stokes wave vectors whereas the difference between the modulus of these two wave vectors accounts for dephasing in vibrational CARS. Furthermore, we demonstrate that the range of operation of time-domain CARS velocimetry is extended by probing pure rotational lines. The predictions are validated by experiments which are performed both in a static gas cell and in a Mach 10 supersonic flow. Received: 30 March 2000 / Revised version: 9 June 2000 / Published online: 13 September 2000     

Theoretical vibrational terms and rotational constants for the 15N substituted isotopologues of N2O calculated using normal hyperspherical coordinates

Variational calculations of the vibrational terms G_v and rotational constants B_v of the ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O and ¹⁵N¹⁵N¹⁶O isotopologues of nitrous oxide are carried out using normal hyperspherical coordinates. The Morse-cosine potential energy surface for N₂O previously determined by the authors by fitting to a set of experimental vibrational frequencies is employed. The G_v and B_v spectroscopic constants calculated for the ¹⁵N substituted isotopologues show an satisfactory agreement with those experimentally observed for a large number of vibrational bands of these isotopologues recently measured. Predicted calculated values of these spectroscopic constants for unobserved vibrational bands of the ¹⁵N substituted isotopologues are given in order to be of help in the identification and characterization of such bands, as a complement to the use of global effective Hamiltonians.     

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.     

Calculations of the vibrational frequency and isotopic shift of UF6 and U2F6

Molecular structure, vibrational frequency and infrared intensity of UF6 are investigated by using the revised Perdew Burke-Enzerhof function with the triple-zeta polarized basis set. The calculation results are in good agreement with the experimental values and indicate the existence of a stable U2F6 molecule with a multiple bonded U2 unit. The calculation results also predict that the D3d symmetry of U2F6 is more stable than D3h. The optimized geometries, vibrational frequencies, and infrared intensities are also reported for U2F6 molecules in D3d symmetry. In addition, the isotopic shift of vibrational frequencies of the two molecules under isotopic substitution of uranium atom are also investigated with the same method. The U2F6 molecule is predicted to be better than UF6 for laser uranic isotope separation.     

Oxygen concentration and temperature measurements in N2–O2 mixtures using rotational coherent anti-Stokes Raman spectroscopy

The accuracy and precision of oxygen concentration and temperature measured by dual-broadband rotational Coherent Anti-Stokes Raman Spectroscopy (CARS) were investigated in nitrogen-oxygen mixtures at atmospheric pressure and temperatures between 290 and 1410 K. The relative standard deviation of temperatures evaluated from pure oxygen rotational CARS spectra was found to be around 5%, and the mean temperature was the same as for nitrogen CARS spectra, except for temperatures above 1000 K, where the temperature was 120 K below the correct value. The in situ calibrated oxygen concentrations were within 10% of the correct value, with a standard deviation of around 1.2% for the mixtures of 12 and 20% oxygen in nitrogen. For the lowest oxygen concentrations considered in this study (2 and 4%), the systematic errors in the evaluated concentrations were very large, and the standard deviation of repeated single-shot measurements was above 2%. However, employing weighting in the spectral fitting routine reduced the errors in the concentration and the single-shot standard deviation was lowered to 0.5%. Finally, it was shown that spectral interference (from oxygen) in a rotational CARS spectrum of nitrogen generally had little impact on the temperature evaluated from fitting the spectra to theoretical nitrogen spectra.     

Discharge ignition phenomena in CO2 and N2O lasers with preliminary filling of the interelectrode gap by electrons

A comprehensive model is presented that describes preionization and discharge ignition processes in large-aperture molecular-gas lasers. By initially filling the interelectrode gap with electrons and establishing a space-charge screen at the cathode, electron avalanche begins adjacent to the anode. Cathode-directed ionization waves develop and ignite the discharge. Dynamic profiling of the electric-field distribution and Penning ionization of a readily ionizable additive combine to decrease both the ignition and quasi-steady-state voltages.     

Comparison of the first negative corona current pulses in N2 + SF6 and CO2 + SF6 mixtures

The current waveforms of the first negative corona pulses in a small point-to-plane gap have been measured with a nanosecond time resolution in N₂ + SF₆ and CO₂ + SF₆ mixtures at a pressure 50 kPa for various contents of SF₆ as a function of applied gap voltages. The physical mechanism for the pulses in these mixtures with low concentration of SF₆ has been described using the streamer-based theory. The influence of changing admixtures of SF₆ in N₂ and CO₂ has been compared. Differences in the pulse waveforms observed in N₂- and CO₂-based gas mixtures are explained by differences in the first and second Townsend ionization coefficients. This work was supported by the Grant Agency VEGA from the Ministry of Education of Slovak Republic under contracts 1/1011/04 and 1/2017/05.     

Excitation of bands of the first negative system of the N 2 + ion in collisions of N+ and O+ ions with N2 molecules

Absolute values of the excitation cross sections of the (0,0) bands [for O⁺(⁴ S), O⁺(² P)-N₂ pairs] and the (0,0), (0,1), (1,2), and (2,3) bands [for N⁺(³ P)-N₂ pairs] of the first negative system of the N ₂ ⁺ ion have been measured in collisions with nitrogen molecules of nitrogen and oxygen ions in the ground state and in a metastable state in the interval of ion energies 1–10 keV. The process of excitation of the (0,0) band of the first negative system of the N ₂ ⁺ ion by oxygen ions in the metastable ² P state is of a quasi-resonant character. The presence in the beam of ions in metastable states was monitored by measuring the excitation efficiency of the (0,0) band λ3914 Å of the N ₂ ⁺ ion in different operating regimes of the highfrequency ion source. For N⁺ ions in the ³ P ground state, as the collision frequency is decreased the relative vibrational population of the v′=1 and v′=2 levels of the B ²Σ _u ⁺ state of the N ₂ ⁺ ion is observed to deviate strongly from the value calculated in the Franck-Condon model.     

Reversible hydrogen-storage functions for mixtures of Li3N and Mg3N2

The hydriding and dehydriding reactions occurring in mixtures of lithium and magnesium nitrides (Li₃N and Mg₃N₂) were investigated for the first time in fixed composition ratios. A mixture of Li₃N–20 at.%Mg₃N₂ after heat treatment at 833 K was hydrogenated at 523 K in 35 MPa according to the following overall reaction: 4Li₃N+Mg₃N₂+12H₂ 12LiH+3Mg(NH₂)₂. This reaction is one of the candidates for reversible hydrogen-storage functions in which 9.1 mass% of hydrogen can be stored in the solid state. PACS 81.05.Zx; 71.20.Ps; 82.30.-b