Fast relaxation of the metastable helium state 2S0 in collisions with molecules and collisional lasing on the He (2P1-2S0) transition

In the present study, the laser absorption method was used to measure the rates of quenching of the metastable state He(2¹S₀), the lower laser level in the self-terminating helium laser, with H₂O, NH₃, N₂O, and CO₂ molecules. For the above molecules, the quenching rate constants were found to equal (1.2 ± 0.3)10^− 9, (0.8 ± 0.2)10^− 9, (1.9 ± 0.2)10^− 9 and (2.2 ± 0.4)10^− 9 cm³ s^− 1. Under excitation with long (up to 750 ns) open discharge generated electron beam pulses, lasing on the transition He (2¹P₁⁰-2¹S₀) was examined. In the mixtures He-H₂O and He-NH₃, lasing durations almost equal to the pump-pulse duration were obtained. In the mixtures of He with CO₂ and N₂O, no lasing prolonged in comparison with pure helium was found. The data obtained were explained considering two quenching mechanisms for the state He(2¹S₀): in collisions with molecules and in collisions with plasma electrons having low energies due to fast relaxation of the vibrational states of H₂O and NH₃ molecules.     

Physical properties of the cubic spinel LiMn2O4

We have performed an ab initio study of structural, electronic, magnetic, vibrational and thermal properties of the cubic spinel LiMn₂O₄ by employing the density functional theory, the linear-response formalism, and the plane-wave pseudopotential method. An analysis of the electronic structure with the help of electronic density of states shows that the density of states at the Fermi level (N (E_F)) is found to be governed by the Mn 3d electrons with some contributions from the 2p states of O atoms. It is important to note that the contribution of Mn 3d states to N(_EF)$N\left(E_F\right)$ is as much as 85%. From our phonon calculations, we have obtained that the main contribution to phonon density of states (below 250 cm⁻¹) comes from the coupled motion of Mn and O atoms while phonon modes between 250 cm⁻¹ and 375 cm⁻¹ are characterized by the vibrations of all the three types of atoms. The contribution from Li increases rapidly at higher frequency (above 375 cm⁻¹) due to the light mass of this atom. Finally, the specific heat and the Debye temperature at 300 K are calculated to be 249.29 J/mol K and 820.80 K respectively.     

碰撞诱导离解(CID)(Ⅱ)——I2(B3∏o+u)在高振动态(v′=62)的碰撞猝灭机理实验研究

本文研究了B³∏_o+u激发态I₂分子在高振动态v′=62时的碰撞猝灭过程。实验中得到了该能级I₂分子和其自身以及与其他气体分子(He,Ar,Kr,H₂,CO,N₂,O₂,CH₄,NH₃,C₂H₆,CCl₄)的碰撞猝灭速率常数,并且发现,在I关键词：     

New high-resolution analysis of the {ν1 + ν3} band of the NO2 isotopomer of nitrogen dioxide: Line positions and intensities

The high-resolution Fourier transform absorption spectrum of an isotopic sample of nitrogen dioxide, ¹⁵N¹⁶O₂, was recorded in the 3.4 μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242 (1991) 367-377] a new analysis of the ν₁ + ν₃ band located at 2858.7077 cm⁻¹ has been performed. This new assignment concerns (1 0 1) energy levels involving rotational quantum numbers up to K_a = 10 and N = 54. Using a theoretical model which accounts for both the electron spin-rotation resonances within each vibrational state and the Coriolis interactions between the (1 2 0) and (1 0 1) vibrational states, the spin-rotation energy levels of the (1 0 1) vibrational state could be reproduced within their experimental uncertainty. In this way, the precise vibrational energy, rotational, spin-rotation, and coupling constants were achieved for the {(1 2 0), (1 0 1)} interacting states of ¹⁵N¹⁶O₂. Using these parameters and the transition moment operator which was obtained for the main isotopic species, ¹⁴N¹⁶O₂, a comprehensive list of the line positions and intensities was generated for the ν₁ + ν₃ band of ¹⁵N¹⁶O₂.     

The ν3 and 2ν3 bands of SO3, SO3, SO3, and SO3

This sixth of a series of publications on the high-resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the ν₃ and 2ν₃ infrared bands of the four symmetric top isotopomers ³²S¹⁶O₃, ³²S¹⁸O₃, ³⁴S¹⁶O₃, and ³⁴S¹⁸O₃. An internal coupling between the l=0(A₁^′) and l=2(E^′) levels of the 2ν₃ states was observed. This small perturbation results in a level crossing between |k−l|=9 and 12, in consequence of which the band origins of the A₁^′,l=0 “ghost” states could be determined to a high degree of accuracy. Ground and upper state rotational constants as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species ³²S¹⁶O₃ and ³⁴S¹⁶O₃ vary only slightly, as do the constants for the ³²S¹⁸O₃, ³⁴S¹⁸O₃ pair. The S-O bond lengths for the vibrational ground states of the species ³²S¹⁶O₃, ³⁴S¹⁶O₃, ³²S¹⁸O₃, and ³⁴S¹⁸O₃ are, respectively, 141.981 99(1), 141.979 38(6), 141.972 78(8), and 141.969 93(8) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.     

Electron spectroscopy using excited atoms and photons IX. Penning ionization of CO2, CS2, COS,N2O,H2S,SO2, and NO2

The electron spectra resulting from thermal collisions of He* (predominantly 2³S) metastable atoms with the seven triatomic molecules, CO₂, COS, CS², N₂O H₂S, SO₂ and NO₂, are compared with their respective 584-Å photoelectron spectra using a transmission-corrected electron spectrometer. The normalised relative electronic-state transition probabilities for production of ionic states in Penning ionization and photoionization are reported together with energy shifts (ΔE values) for He*(2³S) Penning ionization. The cross-section for Penning ionization to lower states of NO₂⁺ is extremely low as has been observed in other open shell molecules such as NO and O₂.     

Room-temperature broadening and pressure-shift coefficients in the ν2 band of CH3D-O2: Measurements and semi-classical calculations

We report measured Lorentz O₂-broadening and O₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band. Using a multispectrum fitting technique we have analyzed 11 laboratory absorption spectra recorded at 0.011 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer, Kitt Peak, Arizona. Two absorption cells with path lengths of 10.2 and 25 cm were used to record the spectra. The total sample pressures ranged from 0.98 to 339.85 Torr with CH₃D volume mixing ratios of 0.012 in oxygen. We report measurements for O₂ pressure-broadening coefficients of 320 ν₂ transitions with quantum numbers as high as J″ = 17 and K = 14, where K″ = K′ ≡ K (for a parallel band). The measured O₂-broadening coefficients range from 0.0153 to 0.0645 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported O₂-induced pressure-shift coefficients vary from about −0.0017 to −0.0068 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%. The O₂-broadening and pressure shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are generally larger than the experimental data. Using for the trajectory model an isotropic Lennard-Jones potential derived from molecular parameters instead of the spherical average of the atom-atom model, a better agreement is obtained with these data, especially for |m| ? 12 values (11.3% for the first calculation and 8.1% for the second calculation). The O₂-pressure shifts whose vibrational contribution are either derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D or those obtained from pressure shifts induced by Xe in the ν₃ band of CH₃D are in reasonable agreement with the scattered experimental data (17.0% for the first calculation and 18.7% for the second calculation).     

Measurement at different temperatures of absolute intensities,line half-widths,and broadening by Ar and N2 for the 3001II←0000 band of CO2

Absolute intensities, self-broadening coefficients, and foreign-gas broadening by Ar and N₂ were measured at temperatures of 197, 233 and 294 K for the 30⁰1_II←00⁰0 band of CO₂ at 6348 cm^-1. Also, the intensity parameters and total band intensity were calculated. We obtained for the vibration-rotation interaction factor the value F(m) = 1 + (0.26 ± 0.06) × 10^-2m + (0.92 ±0.32 × 10^-4 m²; for the purely vibrational transition moment, we found ¦R₀₀₀₀^3001_II¦к(0.4351 ± 0.0014)()10^b3 debye; and, for the total band intensity at STP conditions, S_band(30⁰1_II←00⁰0)_STP = 1255 ± 9 cm^-1 km^-1 atm^-1.Self-broadening coefficients at 197 and 294 K were also measured, as well as broadening by Ar and N₂. Foreign-gas-broadening efficiencies (Ar and N₂) were determined. Finally, a comparison is made with measurements by other authors and with theoretically calculated values.     

Infrared laser magnetic resonance (LMR) spectroscopy of NO2 (ν2) with a CO2 laser

The infrared laser magnetic resonance spectra for the ν₂ band of NO₂ were observed by using a CO₂ laser. High-K vibration-rotation transitions from ^rR₆(N) to ^rR₁₁(N) (v₂ = 1 ← 0) were observed. The analysis yielded some molecular parameters including two g factors for the excited vibrational state (v₂ = 1).     

Measurements and theoretical calculations of N2-broadening and N2-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N₂-broadening and pressure-shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).     

Linewidth and intensity measurements of SO2 lines at 94 GHz with self-broadening and broadening by H2O and N2

In the frequency range between 91.5 and 95.5 GHz, three rotational lines of the ³²S¹⁶O₂ and two rotational lines of the ³⁴S¹⁶O₂ molecules in the fundamental vibrational state, and also two lines of the ³²S¹⁶O₂ molecule in the v₂ vibrational state, have been investigated. Center frequencies and absolute absorptions have been measured and compared with theoretical values. Furthermore, the self-broadening and broadening by H₂O and N₂ of the transition 23(6,18)–24(5,19) with the line center at 94.064 GHz have been investigated. The following linewidth parameters were found: SO₂-SO₂, 18.2±0.3 MHz/torr; SO₂-N₂, 3.8±0.1 MHz/torr; SO₂-H₂O, 15.2±0.2 MHz/torr. The bridge spectrometer and the measuring method used are also described.     

Experimental determination of pressure-broadening parameters of millimeter-wave transitions of HNO3 perturbed by N2 and O2, and of their temperature dependences

We report on linewidth measurements on the J=24_K,11−23_K^′,10 and J=38_K,33−37_K^′,32 millimeter wave transitions in the ground vibrational state of nitric acid, located near 470.23 and 544.36 GHz, respectively. Experiments were performed with N₂ and O₂ as perturber molecules, in the 240-350 K temperature range by using a video-type spectrometer. The foreign-gas broadening parameters and their temperature dependence coefficients were determined using the Voigt profile, no narrowing effect being observed. In order to check the reliability of reported values, we carried out measurements on the J=14_K,12−13_K^′,11 transition located near 206.6 GHz, previously observed in two other laboratories. For this last line all the reported values are consistent themselves within one claimed standard deviation.     

Diode-laser measurements of O2, N2 and air-pressure broadening and shifting of NH3 in the 10 μm spectral region

Using a tunable diode-laser spectrometer, we have measured the O₂, N₂, air-shift and broadening coefficients for 5 lines of ammonia in the R branch of the ν₂ band. These lines are located in the spectral range 1030-1070 cm⁻¹. The pressure shift and broadening are obtained by fitting the measured shapes of these lines by a Voigt profile. The broadening parameters and shift coefficients are compared to the results of theoretical calculations based on the semiclassical Robert-Bonamy formalism (RB) in which the intermolecular potential includes electrostatic, induction, and dispersion energy contributions. The variation of these coefficients with rotational and vibrational quantum numbers is examined. The results are generally in satisfactory agreement with experimental data.     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

Calculation of radiative transition probabilities and radiative recombination rate coefficients for H2, OH, H 2+ and OH+ molecules

A method is presented to calculate the radiative transition probabilities and the radiative recombination rate coefficients between electronic molecular states. Total transition probabilities are determined from vibrational transition probabilities without considering the detailed rotational structure of the molecular electronic states. Radiative recombination rate coefficients are obtained from the computation of vibrational photo-ionisation cross sections. Concerning spontaneous emission, Lyman (B → X) and Werner (C → X) band systems of H₂ and Meinel (A → X), (B → A) and (B → X) band systems of OH are investigated. For radiative recombination, transitions between H₂⁺ (X) and H₂(X), and between OH⁺(X, a, A, b, and c) and OH(X) are considered. Transition probabilities and recombination rate coefficients are calculated as a function of temperature in the range 1500–15 000 K.     

Electronic-excitation transfer collisions in flames—V. Cross sections for quenching and doublet-mixing of K(42P)-doublet by N2, O2, H2 and H2O

Weighted average cross sections for quenching of the K(4²P)-doublet by N₂, H₂, O₂ and H₂O, measured in flames, show no significant temperature dependence in the range from 1500 to 2500K. Doublet mixing cross sections for K(4²P$\text{3}\text{2}$?4²P$\text{1}\text{2}$) transitions were measured at 1720K for N₂, O₂, H₂O. The ratios of both mixing cross sections were measured independently and were found to agree with the detailed balance condition within 2 per cent. It is shown that an ionic intermediate-state model cannot explain the large magnitude of N_2? mixing cross sections.     

Generation of O-2 molecular ions in electron-irradiated KBr and KI crystals

It is shown that during electron irradiation of KBr and KI crystals at 80 K a vibronic structure develops in the emission spectrum characteristic of O^-₂ molecular ions. The origin of these ions is explained in terms of the processes following the radiolysis of OH^- impurity ions. Total disappearance (thermal quenching) of the vibronic structure T#62;170 K for KBr and T#62;110 K for KI is attributed to the reaction between mobile X^-₂ (V_k) centres and O^-₂ molecular ions resulting in the formation of optically inactive O₂ molecules.     

Air-broadening coefficients of the HO2 radical in the 2ν1 band measured using cw-CRDS

In this paper we present measurements of the air-broadening coefficients of HO₂ at room temperature in the 2ν₁ band around 1.5 microns. The HO₂ radicals were created by flash photolysis of SOCl₂ in a flow of O₂/CH₃OH mixtures. To observe air-broadening, N₂ (79%) and O₂ (21%) were added using calibrated flow controllers and a total pressure controller. The total pressure was monitored in parallel using a capacitive pressure gauge. Air-broadening coefficients at 296 K were determined for 34 absorption lines between 6631 and 6671 cm⁻¹. The air-broadening coefficients of HO₂ show a rotational dependence (decreasing from about 0.14 cm⁻¹/atm for N″ = 3 to about 0.09 cm⁻¹/atm for N″ = 10). No evidence for collisional narrowing was observed.     

Self-, N2- and O2-broadening coefficients for the CO2 transitions near-IR measured by a diode laser photoacoustic spectrometer

Using a high-resolution tunable diode laser photoacoustic spectrometer, self-, N₂ and O₂ pressure broadening coefficients for the first 11 transitions of ¹²C¹⁶O₂ in the R branch of the (30012) ← (00001) overtone band at the 6348 cm⁻¹ have been revisited at room temperature (∼298 K). Air-broadening parameters have also been calculated from the N₂ and O₂ measurements. The dependence of the broadening on rotational quantum number m is discussed. The recorded lineshapes are fitted with standard Voigt line profiles in order to determine the collisional broadening coefficients of carbon dioxide transitions. The results are compared to our previous measurements and to the values reported in the HITRAN04 database and by other research group with a different spectroscopic technique.     

Vibrational properties of superionic glasses (AgI)x(Ag2O nB2O3)1-x

In this letter we refer on the Raman-scattering measurements in superionic glasses (AgI)_x(Ag₂O nB₂O₃)_1-x where 0 ? x ? 0.5. The behaviour of the low-frequency Raman spectra, Δν < 250 cm^?1, has been interpreted as due to a vibrational density of states mainly due to the silver halide. Nonlinear increase of the Raman efficiency with the increase of AgI concentration has been found: a phenomenological explanation is presented.