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.     

Photoacoustic measurements of Lorentz broadening in CO2 between 25° C and 450° C

A variable temperature photoacoustic cell has been constructed and tested by studying the interplay of CO₂, H₂O, and NH₃ in synthetic smoke. Saturation effects for CO₂ and NH₃ have been modeled and compared with experiments, and results are obtained for the vibrational relaxation rate associated with NH₃-H₂O collisions. The cell has been used for studying the temperature dependence of self-broadening and N₂ broadening of CO₂ lines. The temperature dependence of the scattering rate is well described by a T ^–n law with n=0.77 in both cases. This result agrees with previous results obtained by tunable diode laser spectroscopy, but disagrees with results obtained by indirect methods.Supported by the Danish Science Research Council under grant no. 11-7777, and by FLS-airloq A/S     

Infrared and Raman spectra of M2Cu2O5 (M=Y,Ho)

We report both Raman and infrared reflectivity spectra of M₂Cu₂O₅ (M=Y, Ho) at room temperature in the spectral range of 30–1000 cm^–1.37 (31) ir and 18 (15) Raman active modes of Y₂Cu₂O₅ (Ho₂Cu₂O₅) are observed. A factor group analysis has been performed to identify the symmetries of the observed modes. Comparing the vibrational spectra of these compounds we conclude that the phonons above 300 cm^–1 originate from the Cu–O vibrations and those under 300 cm^–1 from M–O vibrations.Alexander von Humboldt Foundation fellow     

Infrared absorption and far-infrared diffuse reflection spectra in Pb-doped Bi?Sr?Ca?Cu?O high-temperature superconductor

In this paper we study the room-temperature infrared transmission spectra (400–1600cm^–1) and far-infrared diffuse reflection spectra (50–450cm^–1) in Pb-doped Bi–Sr–Ca–Cu–O (2223) single phase (Tc=107k, sp1), multiphase (Tc=110k, sp2) and nonsuperconducting samples (sp3). The spectral features in superconductor are totally different from those in nonsuperconductor, which show the different crystal structure. The correlation existing between a factor group analysis of the phonons in (2223) and (2212) compounds affords a tentative assignment of ir-active modes in Pb-doped (2223) single phase by comparison with reported data in (2212) materials. The Cu–O stretching E_u vibration (605cm^–1) of CuO₂ layers is the characteristic vibrational mode related perovskitelike crystal structures. Two phonon coupling effect emerges in the infrared transmission spectra in Pb-doped superconductor. The Ca–O vibration A_2u (254cm^–1) might be related to superconductivity of Bi-based family.     

Water Vapor Measurements between 590 and 2582 cm: Line Positions and Strengths

This study involves measurements of H₂¹⁶O, H₂¹⁷O, and H₂¹⁸O vapor spectra for the region between 590 and 2582 cm⁻¹. The parameters derived from the data include line positions, energy levels, and linestrengths. The study involves high-resolution line-position measurements with samples at room temperature in the (000)–(000), (010)–(010), and (010)–(000) bands. The experimental frequencies were used along with microwave, far-infrared, and hot water emission measurements in an analysis to obtain high-accuracy rotational energy level values in the (000), and (010) vibrational states of H₂¹⁶O forJ≤ 20. The experimental linestrengths were fitted by least squares to a model in which the dipole moment was represented as a series expansion containing up to 19 dipole moment matrix elements. The measurements in this work were more extensive than reported in prior studies by this author for the (010)–(000) band.     

Neon matrix isolation spectroscopy of CO2 isotopologues

The solid neon matrix isolated spectrum of CO₂ are recorded in the 2–5 μm region. Natural and ¹³C or ¹⁸O enriched CO₂ samples were used and the nν₁ + ν₃ (n = 0, 1, 2) series bands of different CO₂ isotopologues have been observed. The solid neon matrix shift due to Fermi-resonance of bands within the same vibrational polyad is analyzed.     

The rotational Raman spectra and cross sections of H2O, D2O, and HDO

We report the experimental rotational Raman spectra of H₂O, and of a mixture of D₂O and HDO in the vapor phase at room temperature, and their interpretation in terms of rotational–vibrational energies, wavefunctions, and transition moments of the molecular polarizability. These transition moments are based on high-level ab initio calculations of the wavelength dependent polarizability surface, and on wavefunctions where the rotational–vibrational coupling is considered in detail. As a byproduct of this analysis several tables have been compiled including scattering strengths and assignments for individual rotational transitions of the three species. From these tables the rotational Raman spectra can be simulated over the range of temperatures up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Vibrational kinetics of the active media of CW CO<Subscript>2</Subscript> lasers

The vibrational kinetics of CW CO₂ lasers has been analyzed within the framework of a temperature model. The necessity of taking into account the coupling of the vibrational modes of the CO₂ molecule in determining the occupation numbers and the store of vibrational energy in individual modes is shown. Expressions that connect vibrational temperatures with the rates of excitation and relaxation of the lower vibrational levels of modes have been obtained. The ratios between the vibrational temperatures on selective excitation of the 00° 1 level and on excitation of CO₂ molecules in an electric discharge as well as the character of the dependences of vibrational temperatures on the pumping-energy value are discussed.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 72–79, January–February, 2005.     

Application of the method of energy moments to an analysis of the rotational and centrifugal constants of the H2O molecule

A method is described to compute the centrifugal constants from the first and second order energy moments. Presented as an illustration is a computation of the centrifugal constants of the H₂O molecule for the 000 vibrational state; conditions proposed in [2] were imposed on the parameters of the unitary transformation; the centrifugal constants obtained under such conditions reproduce the spectrum to 0.1 cm^–1 accuracy.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 80–84, August, 1973.     

Submillimeter-wave spectroscopy of HCN in excited vibrational states

Measurements of the rotational spectrum of HCN in excited vibrational states have been extended to higher-J values. The transitions reach J=8←7 around 710 GHz for most vibrational states studied in this investigation and J=22←21 near 2 THz for the (020) and (030) vibrational states. Using a pure sample of gaseous HCN at 350 K, selected states up to one quantum in the C–H stretching vibration at 3311.5 cm⁻¹ have been investigated. Even transitions having two quanta in the C–H stretch could be studied employing a glow discharge in a gas mixture of CH₄ and N₂. Molecular constants in 13 vibrational states have been obtained, several of which have been studied for the first time by rotational spectroscopy. The vibrational temperature in the discharge system is found to be about 1500 K for the stretching vibrational modes and about 600 K for the bending states.     

Rotational spectra of mono-substituted asymmetric C6H6-H2O dimers

This paper reports the assignment of the rotational spectra of the m = 0 and 1 states of ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers. The m = 1 progression was not identified or assigned for both ¹³CC₅H₆-H₂O and C₆H₅D-H₂O in the earlier work, though for the symmetric isotopomers (C₆H₆-H₂O/D₂O/H₂¹⁸O), they were identified [H.S. Gutowsky, T. Emilsson, E. Arunan, J. Chem. Phys. 99 (1993) 4883]. The m = 1 transitions for ¹³CC₅H₆-H₂O and C₆H₅D-H₂O were split into two, unlike that of the parent C₆H₆-H₂O isotopomer. The splitting varied, somewhat randomly, with quantum numbers J and K. The m = 0 lines of ¹³CC₅H₆-H₂O had significant overlap with the m = 1 lines of the parent isotopomer, clouding proper assignment, and leading to an rms deviation of about 200 kHz in the earlier work. The general semi-rigid molecular Hamiltonian coupled to an internal rotor, described recently by Duan et al. [Y.B. Duan, H.M. Zhang, K. Takagi, J. Chem. Phys. 104 (1996) 3914], is used in this work to assign both m = 0 and 1 states of ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers. Consequently, the m = 0 fits for ¹³CC₅H₆-H₂O/D₂O have an rms deviation of only 4/7 kHz, comparable to experimental uncertainties. The fits for m = 1 transitions for ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers have an rms deviation of about 200 kHz. However, it is of the same order of magnitude as that of the m = 1 state of the parent C₆H₆-H₂O dimer. The A rotational constants determined from the m = 0 fits for both ¹³CC₅H₆-H₂O and ¹³CC₅H₆-D₂O isotopomers are identical and very close to the C rotational constant for ¹³CC₅H₆. This provides a direct experimental determination for the C rotational constant of ¹³CC₅H₆, which has a negligible dipole moment.     

Stable bonds and unstable bonds in Y(Pr)-123 system

The Pr content dependence of the bond lengths of Y–Cu, Y–O, O–O, Cu–O, Ba–Cu and Ba–O in PrBa₂Cu₃O_y are analyzed and discussed in detail. The different valence bonds can be divided into two groups: stable bonds and unstable bonds. Since the bond lengths and angles between every two ions among O2, Cu2 and O3 are very stable, we conclude that the three ions form an unchangeable triangle when the Pr doping changes. The triangle is called “fixed triangle”. This “fixed triangle” can slightly rotate around the Cu2 ions. It is just this rotation that leads to the unstable bonds. As the increase of the Pr content, the bond lengths between the two Cu(2)–O planes becomes larger and larger, the Cu(2)–O planes bend towards the Ba–O plane. The bonds lengths between the Cu(2)–O and Ba–O planes vary oppositely from those of Cu(2)–O, and become shorter and shorter. These changes connected with the superconductivity are discussed.     

Radical-Recombination Luminescence of the Uranyl Nitrate Complex in the Adsorbed State

We have investigated the luminescence of uranyl nitrate molecules on the surface of powdery SiO₂ upon excitation by UV light (PhL) and hydrogen atoms (radical-recombination luminescence (RRL)). It has been found that the PhL and RRL spectra have a clearly defined vibrational structure. The luminescence peaks of the adsorbed UO₂ ^2– ion are characterized by a systematic longwave shift from the same peaks of crystalline uranyl nitrate (by 230–430 cm^–1 at 130 K). Moreover, in the adsorption centers the vibration frequencies of UO₂ ^2– are 20–80 cm smaller than in crystalline salt and the RRL bands are 150–350 cm^–1 (130 K) wider than the corresponding PhL bands.     

Fourier transform emission spectroscopy of the TiF radical in the 407 nm region

Ultraviolet emission spectra of the TiF radical in the 407 nm region have been observed at a resolution of 0.04 cm⁻¹ using a Fourier transform spectrometer. A new electronic assignment of ⁴Γ–X⁴Φ has been proposed. Rotational analysis has been obtained for the 0–0 and 1–1 vibrational bands of the ⁴Γ_5/2–X⁴Φ_3/2, ⁴Γ_9/2–X⁴Φ_7/2, and ⁴Γ_11/2–X⁴Φ_9/2 subbands and the 0–0 band of ⁴Γ_7/2–X⁴Φ_5/2. The lower state rotational and centrifugal distortion constants are consistent with the previous results [J. Mol. Spectrosc. 184 (1997) 186; J. Chem. Phys. 119 (2003) 9496], to the conformation that the lower state of the 407 nm band is the ⁴Φ ground electronic state. Rough estimates of the vibrational interval ΔG(1/2) and the spin–orbit coupling constant A in the ⁴Γ state were also obtained.     

The ν1 and ν3 Bands of the OOO Isotopomer of Ozone

Using 0.002 cm⁻¹ resolution Fourier transform absorption spectra of an ¹⁷O-enriched ozone sample, an extensive analysis of the ν₃ band together with a partial identification of the ν₁ band of the ¹⁷O¹⁶O¹⁷O isotopomer of ozone has been performed for the first time. As for other C_2v-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3–16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers ν₀(ν₃) = 1030.0946 cm⁻¹ and ν₀(ν₁) = 1086.7490 cm⁻¹ were obtained for the ν₃ and ν₁ bands, respectively.     

Vibrational Spectra and Structure of Potassium Alum Kal(SO4)2·12[(H2O) x (D2O)1−x ]

The IR spectra and polarization Raman spectra of Kal(SO₄)₂·12(H₂O) and Kal(SO₄)₂·12[H₂O)_0.3(D₂O)_0.7] crystals at 93 K and room temperature have been obtained experimentally. The vibrational spectra of structural elements of potassium alum — the complexes [Al(H₂O)₆ ³⁺ and [Al(D₂O)₆]³⁺ — have been calculated. The vibrational spectra have been interpreted based on the calculation and factor-group analysis data. The spectral data obtained point to the fact that, in the crystals considered, the sulfate ions are partially disordered and there exist two crystallographically different types of water molecules.     

Effect of vibrational kinetics of He2 + ions on the afterglow of a discharge in helium

A decaying weakly ionized helium plasma [n_e=(0.2–1.1)·10¹¹ cm^–3, p=(40–70) mm Hg] was studied experimentally. It is shown that the experimental time dependences of the intensities of atomic lines and molecular bands in the afterglow phase can be explained if the vibrational kinetics of He₂ ⁺ ions is included in the analysis. Analysis of the measurements shows that for n_e 10¹¹ cm^–3 and N_a 10¹⁸ cm^–3 deexcitation of He₂ ⁺ ions occurs primarily as a result of inelastic collisions with helium atoms. Based on the experimental data, an approximate value was obtained for the rate constants of the vibrational relaxation of molecular helium ions 10^–16 cm³/sec. These results are used for making a qualitative analysis of the distribution of He₂ ⁺ ions over the vibrational states in the discharge phase.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 88–96, November, 1986.     

Influence of molecular relaxation dynamics on quartz-enhanced photoacoustic detection of CO2 at λ =2 μm

Carbon dioxide (CO₂) trace gas detection based on quartz enhanced photoacoustic spectroscopy (QEPAS) using a distributed feedback diode laser operating at λ=2 μm is performed, with a primary purpose of studying vibrational relaxation processes in the CO₂-N₂-H₂O system. A simple model is developed and used to explain the experimentally observed dependence of amplitude and phase of the photoacoustic signal on pressure and gas humidity. A (1σ) sensitivity of 110 parts-per-million (with a 1 s lock-in time constant) was obtained for CO₂ concentrations measured in humid gas samples. PACS 07.07.Df; 42.62.Fi; 82.80.Kq; 42.55.Px     

HF Laser Based on Thermal- and Photon-Branched Chain Reactions Initiated by IR Laser Radiation

A chemical H₂–F₂ laser (oscillator and amplifier) initiated by means of IR radiative excitation of vibrational levels of HF molecules is studied under the conditions of development of a thermal-branched chain reaction caused by thermal dissociation of gaseous additions to the laser mixture. It is shown that, using F₂SO₃ addition at a partial pressure of 40 Torr, an H₂–F₂ laser with a mixture pressure of 1~bar initiated by a pulsed hydrogen fluorine laser can provide an output exceeding 120–200 J/liter in 20–50 ns laser pulses.     

CARS studies of vibrationally excited nitrogen at low pressures

Coherent anti-Stokes Raman spectroscopy (CARS) was used to measure the vibrational temperature of microwave-excited nitrogen in a N₂–CO–He mixture. CARS spectra, originating from the N₂-vibrational levelsv=0 up tov=3, have been recorded by both narrowband scanning of the resonance region as well as by broadband OSA detection. For the microwave-excited N₂ molecules a vibrational temperatureT _v (N ₂ = (2130±110K) and a lower limit of detection forN ₂(v = 3) = 1.2 x 10¹⁵ cm^–3 was established. The CARS results were independently confirmed by simultaneously recorded and spectrally resolved CO infrared fluorescence studies.