Microwave spectrum of the hydrogen sulfide molecule H232S in the ground state

Frequencies, line strengths, and intensities of microwave electric dipole rotational transitions of H₂³²S in the ground state have been calculated. The calculation was based on representation of the effective rotational Hamiltonian operator in the form of a Pade operator. As initial information, all known microwave data on frequencies of rotational transitions of H₂³²S in the ground state were used. Some of these data were obtained in the present paper.     

Line strength and halfwidth measurements from far infrared absorption spectra: Carbon monoxide

A method for deriving Lorentzian line shape parameters (line strengths and halfwidths) from absorption spectra taken at two different path lengths is discussed. Far i.r. absorption spectra of carbon monoxide are analysed to yield line strengths and halfwidths for the rotational transitions J″ = 3 through J>″ = 9. Experimental errors are discussed, and the value for the dipole moment derived from the line strengths, 0·108±0·005 D, is in agreement with the microwave value within experimental uncertainty. The Lorentzian halfwidths are compared, where appropriate, with two recent determinations of these quantities. Lorentzian halfwidths are also derived from absorption spectra taken at long path length using theoretical line strengths based upon μ_co = 0·112D.     

A line list of allowed and forbidden rotational transition intensities for water

Pure rotational lines are important for monitoring water concentrations in many environments both in space and on earth. A list of line intensities of rotational transitions for H₂¹⁶O is calculated using variational nuclear-motion wave functions and an ab initio dipole moment surface. This methodology should be equally reliable for both allowed and forbidden rotational transitions. Extensive comparisons are made with available intensity data for these transitions including the HITRAN and JPL databases. Problems are identified with some of these data. A list of 555 allowed and 846 forbidden rotational transition lines within the ground vibrational state is made available.     

Einstein A-coefficients for rotational transitions in the HN2O+

EinsteinA-values for the electric dipole transitions between the rotational levels up to 540 cm⁻¹ andJ=11 in the ground vibrational state of the protonated N₂O (i.e., HN₂O⁺) are calculated. The coefficients are used to compute the mean radiative lifetimes of the levels. TheseA-values can be used for analysing the spectra from astronomical objects, if observed.     

Measurements of N2-broadening and -shifting parameters of the water vapor spectral lines in the second hexad region

The water vapor line broadening and shifting in the ν₁+ν₂+ν₃ band induced by nitrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer at the spectral resolution of 0.01 cm⁻¹ for the line with upper states angular momentum up to 11. Line contour parameters are calculated using a semi-empirical approach extended by the use of empirical data to determine some fitting model parameters. We use the complete set of high accuracy vibration-rotation dipole transition moments calculated for all possible transitions using wavefunctions determined from variational nuclear motion calculations and an ab initio dipole moment surface. Calculated values of line contour parameters are in a good agreement with observed parameters.     

Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

Structure and symmetry of azulene as determined from microwave spectra of isotopomers

The rotational spectra of six ¹³C isotopomers in natural abundance and of eight synthesized deuterium isotopomers of azulene have been measured using pulsed nozzle cavity and waveguide Fourier transform microwave (FTMW) spectrometers over the 8–18?GHz range. The spectrum of the parent species was remeasured with the higher resolution of FTMW spectrometers. Rotational constants have been fitted to the measured frequencies of the rotational transitions of all measured isotopomers. In addition, centrifugal distortion constants were determined for the parent species and the deuterated isotopomers. The permanent electric dipole moment was redetermined from Stark splittings. The C_2v covering symmetry of the azulene molecule has been demonstrated unambiguously from a single set of observed transitions for the asymmetrically substituted 1-, 4-, 5- and 9-¹³C–isotopomers at twice the intensity of the symmetrically substituted 2- and 6-¹³C–isotopomers. The positions of all nuclei of the planar non–alternating aromatic ring system of azulene have been determined from moments of inertia of all available isotopomers. Different methods have been used to arrive at a near equilibrium structure.     

Calculation of absorption coefficient for the ν1 band of sulfur dioxide

The absorption coefficients S/d of sulfur dioxide have been calculated for the ν₁ band for temperatures from 300 ～ 1500°K, taking the major isotopic species S³⁴O₂ into consideration. The total number of the vibrational transitions considered were 4, 10, 23, 41 and 70 for the temperatures of 300, 600, 900, 1200 and 1500°K, respectively. The vibrational energy was calculated to the second order, and the rotational energy and matrix element were calculated exactly with consideration for the asymmetry of the sulfur dioxide molecule. The line intensities greater than 1·0 × 10^-8 cm^-2 atm^-1 STP were included in the calculations. The wavenumber regions of 1000 ～ 1300 cm^-1 were divided into small intervals of Δω = 10 cm^-1 and the S/d averaged over the Δω were obtained. The S/d and some of the line intensities and positions at 300°K were compared with the experimental results of other workers and good agreement was obtained.     

Low rotational transitions of the CF3H molecule: The pressure-induced shift and broadening

Using a microwave spectrometer with a radioacoustic signal detection, the absorption profiles in the multiplets of the low rotational transitions J’?J = 2?1, 3?2, 4?3, and 5?4 of the ¹²CF₃H molecule in the ground vibrational state at pressures of pure gaseous CF₃H from 0.1 to 1.3 Torr when all the K components of the multiplets merge into a single spectral line are studied. The parameters of the pressure-induced shift and broadening of the observed lines are determined by comparing the theoretically modeled absorption signal and the experimental spectrum. The model used takes into account weak lines corresponding to the excited vibrational states v₃ and v₆ of the ¹³CHF₃ molecule and the instrumental features of the spectrometer. The observed multiplet is simulated as an isolated Lorentzian line and as a sum of the profiles of the K components with known unshifted positions and known amplitude ratio. The shift and broadening parameters obtained in both cases are shown to agree well with each other. The dependences of the shift and broadening parameters on the quantum number J are analyzed and compared with the previously obtained data for the lines J’?J = 1?0 and 2?1.     

The structure and helicity of perfluorooctanonitrile, CF3–(CF2)6–CN

New molecular structural data is presented for a cyanide terminated oligomer of polytetrafluoroethene. The target molecule, CF₃–(CF₂)₆–CN, has been seeded within a pulsed supersonic expansion of argon. The result of this action is to cool the species to rotational temperatures below 4 K. Within this state, the pure rotational spectrum of the oligomer has been recorded using two types of Fourier transform microwave spectroscopy. A total of 111 transitions have been identified involving rotational J levels between 6 and 40. Only a- and b-type transitions were observed. The spectrum has been analyzed using a Hamiltonian containing all three rotational constants and one centrifugal distortion constant, D_J. The experimental spectroscopic constants have been used to develop an effective molecular structure by scaling the quantum chemical calculated structure. The data shows that the seven carbon perfluorinated chain for the isolated oligomer twists ≈104°. This compares well to the C₇F₁₃-twist of ≈97° anticipated from the X-ray structure of phase II polytetrafluoroethene.     

Electroabsorption near the 1S line of the green series of Cu2O

The effect of an electric field on the n = 1 line of the green series of Cu₂O has been studies at 4.2°K, using single crystals, polarized light and a modulation technique. Under the action of an electric field, an ignition of this line (λ^g_1S = 5 830 Å) is observed. This ignition effect depends on the geometry of the experiments, and gives informations on the nature of this transition as well as on the bands involved in the formation of this exciton.     

Faraday rotation in single crystal erbium iron garnet

Measurements of the Faraday rotation of ErIG, Er₃Fe₅O₁₂, have been performed in the 4.2–300 K temperature range in magnetic field up to 20 kOe applied along the [111] direction and at 1.15 μm wavelength. The results are analysed under the assumption that the contribution of the Fe³⁺ ions to the total Faraday rotation is the same as that of YIG, Y₃Fe₅O₁₂. The temperature and field dependences of the contribution of the Er³⁺ ions are deduced. Both magnetic and electric dipole contributions of the Er³⁺ ions are calculated; the electric dipole coefficient C_e is found to present a linear temperature dependence between 30–300 K. The temperature dependence of the Faraday rotation susceptibility differs strongly from that of the magnetic susceptibility.     

Magnetic circular dichroism of transition metal ions in solids-I. MgO:Cr3+

Absorption and magnetic circular dichroism (MCD) spectra of MgO: Cr³⁺ have been studied over the temperature range 5–300 °K and with magnetic fields up to 77 kG. A theory for intensity calculation using a weak field coupling scheme is discussed. Spin-forbidden transitions to ²E and ²T₁, are observed in MCD and are interpreted as magnetic dipole zero-phonon lines. The spin allowed bands ⁴T₂ and ⁴T₁ are found to be vibration-induced electric dipole transitions in which the t_1u lattice modes are the dominant contributors to the intensity.     

Rotational and Vibrational Temperature Measurements in a High‐Pressure Cylindrical Dielectric Barrier Discharge (C‐DBD)

The rotational (T_R) and vibrational (T_v) temperatures of N₂ molecules were measured in a high‐pressure cylindrical dielectric barrier discharge (C‐DBD) source in Ne with trace amounts (0.02 %) of N₂ and dry air excited by radio‐frequency (rf) power. Both T_R and T_v of the N₂ molecules in the C ³Π_u state were determined from an emission spectroscopic analysis the 2^nd positive system (C ³Π_u → B³Π_g). Gas temperatures were inferred from the measured rotational temperatures. As a function of pressure, the rotational temperature is essentially constant at about 360 K in the range from 200 Torr to 600 Torr (at 30W rf power) and increases slightly with increasing rf power at constant pressure. As one would expect, vibrational temperature measurements revealed significantly higher temperatures. The vibrational temperature decreases with pressure from 3030 K at 200 Torr to 2270 K at 600 Torr (at 30 W rf power). As a function of rf power, the vibrational temperature increases from 2520 K at 20 W to 2940 K at 60 W (at 400 Torr). Both T_R and T_v also show a dependence on the excitation frequency at the two frequencies that we studied, 400 kHz and 13.56 MHz. Adding trace amounts of air instead of N₂ to the Ne in the discharge resulted in higher T_R and T_v values and in a different pressure dependence of the rotational and vibrational temperatures. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Recommended conventions for defining transition moments and intensity factors in diatomic molecular spectra

Two recommendations are made that can eliminate persistent confusion in the study of diatomic spectroscopy by providing uniform and consistent definitions of the electronic transition moments and the rotational line intensity factors. First, it is recommended that the equation for the line strength of a single rotational line be adopted to specify the relationship between the electronic transition moment and the rotational line intensity factor. Second, it is recommended that the electronic transition moment operator for perpendicular transitions be defined by (1/2^1/2)(μ_x ± iμ_y). The adoption of these conventions results in a value of (2S + 1)(2J + 1) for the sum rule of the rotational line intensity factor for Σ^± ↔ Σ^± transitions and a value of 2(2S + 1)(2J + 1) for the sum rule for all other spin-allowed transitions.     

Solvent effect in monoclinic to hexagonal phase transformation in LaPO4:RE (RE=Dy, Sm) nanoparticles: Photoluminescence study

Nanosized phosphor materials, LaPO₄:RE (RE=Dy³⁺, Sm³⁺) have been synthesized using water, dimethyl sulfoxide (DMSO), ethylene glycol (EG) and mixed solvents at a relatively low temperature of 150 °C. X-ray diffraction (XRD) study reveals that as-prepared nanoparticles prepared in DMSO and EG are well crystalline and correspond to monoclinic phase. In the mixed water-DMSO or water-EG solvents, XRD patterns are in good agreement with hexagonal phase, but transformed to monoclinic phase at higher temperature of 900 °C. TEM images show well-dispersed and rice-shaped nanoparticles of diameter 5-10 nm, length of 13-37 nm for Dy³⁺-doped LaPO₄ and diameter of 25-35 nm, length of 73-82 nm for Sm³⁺-doped LaPO₄. Dy³⁺-doped LaPO₄ shows two prominent emission peaks at 480 and 572 nm corresponding to ⁴F_9/2→⁶H_15/2 (magnetic dipole) and ⁴F_9/2→⁶H_13/2 (electric dipole) transitions, respectively. Similarly, for Sm³⁺-doped LaPO₄, three prominent emission peaks at 561, 597 and 641 nm were observed corresponding to ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2 (magnetic dipole) and ⁴G_5/2→⁶H_9/2 (electric dipole) transitions, respectively. The luminescence intensity of the sample prepared in EG is more than that of DMSO or mixed solvents. Enhancement of luminescence is also observed after heat-treatment at 900 °C due to removal of quencher such as water, organic moiety and surface defects/dangling bonds. The samples are re-dispersible in polar solvent and can be incorporated in polymer film.     

Absorption coefficients for hydrogen—II. Calculated pressure-induced H2–H2 vibrational absorption in the fundamental region

The coefficient for pressure-induced vibrational absorption in H₂ndash;H₂ collisions was calculated for temperatures from 298 to 7000°K and wave numbers between 100 and 40,000 cm⁻¹ for local thermodynamic equilibrium. Because only transitions with a net change of +1 vibrational quanta were considered, the absorption was centered near the fundamental at 4161 cm⁻¹ in the infrared. The model included electronic configuration interaction, mechanical anharmonicity, vibration-rotation interaction, excited vibrational states, and more realistic intermolecular potential and line shapes than previously used. The integrated absorption coefficient at 3000°K was 2.1 times the previous theoretical value. An approximate formula for the absorption coefficient is given for rapid calculation.