New far infrared laser lines from 13CH2F2 and frequency measurements

We report new FIR laser lines from ¹³CH₂F₂ molecules optically pumped by a waveguide CO₂ laser. The increased tunability (300 MHz) with respect to a conventional CO₂ laser allows the pumping of ¹³CH₂F₂ vibrational transitions of large offset. 34 new laser lines have been discovered, ranging from 113.1 m to 491.4 m in wavelength, thus increasing the number of known FIR laser lines from this important molecule to 99. For all the new lines and many (36) of those known previously, precise offset measurements through the transferred Lamb-dip technique were performed. The frequency of six new laser lines was also directly measured by heterodyne detection with known laser lines.     

Design of molecular FIR lasers frequency tunable by stark effect: Electric breakdown of CH3OH,CH3F,CH3I and CH3CN1

The operation of optically pumped FIR molecular lasers in the presence of a static electric field up to 6.5 kV/cm is reported. Wide frequency tuning ranges are demonstrated for the strong CH₃F 496 μm, CH₃I 508 μm, CH₃OH 70.5, 96.5 and 119 μm lines. New Stark tuned lines at about 204 μm are also reported from CH₃OH. A Stark frequency tuning range 75 times larger than the Doppler linewidth is measured. The limitations due to the electrical breakdown in the gas and to the Stark detuning of the pump transitions are investigated. The Paschen curves of CH₃OH, CH₃I, CH₃F and CH₃CN are measured and design parameters for high efficiency Stark tuned FIR molecular lasers are given.     

Confirmation of far infrared laser assignments from CH3-deformation and CH3-rocking states of optically pumped methanol

High-resolution Fourier transform spectroscopy has been applied to confirm previously proposed assignments for nine far infrared (FIR) laser lines from the CH₃-deformation state of CH₃OH and one line from the CH₃-rocking state. Accurate frequencies are deduced for the observed and other predicted FIR laser transitions. FIR torsional branch frequencies in the ground state which were used in the confirmation are presented. Comments are also made on the OH-bending mode of CH₃OH.     

Diagnostics of pulsed molecular beams and free jets with pyroelectric detectors and TEA CO2 lasers

A pyroelectric detector with a time resolution of 3–5 s and a TEA CO₂ laser have been used in diagnostics of a pulsed molecular beam (a free jet). The kinetic energy distribution of molecules was determined by using time-of-flight measurements both with a laser and without it. A combination of the laser with the pyroelectric detector makes it possible to determine the kinetic energy distribution of molecules in a selected internal state and to measure the energy absorted by the molecules of the beam from a laser pulse. The results obtained for pure SF₆ and the SF₆ seeded in He have been presented and analyzed. The advantages and the disadvantages of the method are being discussed in comparison with other available methods of diagnostics of molecular beams and free jets.     

Stark effect on CH3OH and CH3F FIR lasers: Large frequency tuning and resolved structures

The operation of a cw FIR laser in the presence of a strong electric field is described. A hybrid metal-dielectric waveguide is used and the cavity length is scanned to study how the frequency and power of the laser depend on the field strength. The results have also been checked by heterodyning with a conventional reference laser. We report the results obtained for the 496 μm line of CH₃F and the 70.5 μm and 119 μm lines of CH₃OH. A large frequency tunability of almost ±40 MHz is obtained in the best case with power levels in the mW range. A very simple theoretical model accounts for the experimental results. We also report the appearance of a new FIR line at about 204 μm when CH₃OH is pumped by the 9 μmP(34) of CO₂ in the presence of an electric field larger than 1.2 KV/cm.     

3.508 μ-HeXe-laser line absorption by CH3COOCH3, CH3, and NO2 and infrared emission at 6.89 μ by CH3COOCH3 and CH3 at elevated temperatures

Shock-tube HeXe-laser absorption data at ω_L=2850.633 cm^-1 for CH₃COOCH₃ at 757≤T, °K≤1344, NO₂at 412≤T, °K≤1859, andCH₃at 1283≤T, °K≤1562 are presented. Approximate models are used for the effective spectral absorption coefficient of vibration-rotation lines for analytical representations of the results around atmospheric pressures. For CH₃COOCH₃, an equivalent Voigt-profile for an isolated line was adopted in order to account for a dependence on total pressure of the laser absorption coefficient. Shock-tube emission data at λ=6.890 μ(Δλ=0.197μ) forCH₃COOCH₃at 814≤T, °K≤1651 and for CH₃at 1377≤T, °K≤1562 in the v₄-fundamental of the H-bond bending mode of the CH₃-group are well described at atmospheric pressures by approximations of just-overlapping-line models for polyatomic molecules. The adopted models are useful for concentration-time history measurements of methyl acetate, nitrogen dioxide, and methyl radicals behind shock waves.     

An ab initio study of vibrational corrections to the electrical properties of the fluoromethanes: CH3F,CH2F2, CHF3 and CF4

Accurate SCF and MP2 quartic property hypersurfaces have been computed for the energy, dipole moments, quadrupole moments and polarizability tensors of the fluorinated methanes CF₄, CHF₃, CH₂F₂ and CH₃F, to establish accurate values of zero-point vibrational corrections to the properties. Using a consistent set of r_e geometries from density functional theory, these ZPVCs are coupled with accurate electrical properties computed using a range of correlated methods, especially BD and BD(T), and a number of purpose-built polarized basis sets, to obtain near definitive estimates of these properties that incorporate the effects of vibrational averaging. Careful attention has been paid to a critical comparison between these theoretical estimates and experimental measurements, and agreement between the two is shown to be exceptionally good. In particular, it is clear that in many instances more precise experimental results would be required in order to discriminate between different correlated results, or between the present results and those which may be obtained with larger basis sets. The work highlights the necessity to allow for the effects of zero-point vibrational averaging when comparing theory with experiment, or even when comparing different theoretical results with one another using experiment as a benchmark. It also points to the need for further precise experimental measurements of some of these properties.     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

Observation and assignment of submillimetre laser lines from CH3OH pumped by isotopic CO2 lasers

New laser lines have been generated using methanol when isotopically labelled CO₂ is used in the pump laser. 19 lines have been found when¹³C¹⁶O₂ is used and 29 when¹²C¹⁸O₂ is used. The wavelengths of the emission lines have been measured with a relative accuracy of 5×10^–3 using the submillimetre resonator as a scanning Fabry-Perot interferometer, and the polarizations of the lines have also been measured. Some of the laser lines have been assigned to pure rotational transitions in the excited state associated with the CO stretching mode, other lines are believed to originate from pumping in combination bands.     

New cw optically pumped FIR emissions in HCOOH,D2CO and CD3Br

New FIR emissions lines have been observed for HCOOH, D₂CO and CD₃Br. Assignments have been made of the HCOOH lines and for most of those of CD₃Br. For D₂CO, most of the new emissions showed a corresponding cascade transition.     

Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH2SCH2CH3, CH3SCH(OH)CH3, CH3SCH2CH2OH,and radicals corresponding to loss of H atom

Sulfide alkoxy radicals are important intermediates during the partial oxidation of alkyl sulfides in atmospheric chemistry and in combustion. The atmospheric reaction sequence to formation of the alkoxy radicals includes (1) initial reaction with OH to create a radical on a carbon site, (2) the carbon radical then associates with ³O₂ to form a peroxy radical, and (3) an NO radical reacts with the peroxy radical to form an alkoxy radical (RO?) plus NO₂. This study determines structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (Δ_fH°, S°, and C_p(T)) of 3 corresponding alcohols HOCH₂SCH₂CH₃, CH₃SCH(OH)CH₃, and CH₃SCH₂CH₂OH of methyl ethyl sulfides studied in order to characterize the thermochemistry of the respective alkoxy radicals. The lowest energy molecular structures were calculated using the B3LYP density functional level of theory with the 6‐311G(2d,d,p) basis set. Standard enthalpies of formation (Δ_fH°₂₉₈) for the radicals and their parent molecules were calculated using B3LYP/6‐31 + G(2d,p), CBS‐QB3, M062x/6‐311 + g(2d,p), and G3MP2B3 methods. Isodesmic reactions were used to determine ?_fH° values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31 + G(d,p) level theory. The contributions for S°₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by CBS‐QB3 calculations, with contributions from torsion frequencies replaced by internal rotor contributions. Group additivity and hydrogen bond increment values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxide molecules and their radicals.     

Structural and thermochemical studies on CH3SCH2CHO,CH3CH2SCHO,CH3SC(═O)CH3, and radicals corresponding to loss of H atom

CH₃SCH₂CHO, CH₃CH₂SCHO, and CH₃SC(═O)CH₃ are intermediates during the partial oxidation of CH₃SCH₂CH₃ in the atmosphere and in combustion processes. Thermochemical properties (ΔH_f^o, S^o and C_p(T)), structures, internal rotor potentials, and C─H bond dissociation energies of the parent molecules and their radicals formed after loss of a hydrogen atom are of value in understanding the oxidation processes of methyl ethyl sulfide. The lowest energy molecular structures were initially determined using the density functional B3LYP/6‐311G/(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods using isodesmic reactions. Internal rotation potential energy diagrams and internal rotation barriers were investigated using B3LYP/6‐31 + G(d,p) level calculations. The contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation on the basis of the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions from the method of Pitzer‐Gwinn. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CHO, CH₃CH₂SCHO, and CH₃SC(═O)CH₃ are ?34.6 ± 0.8, ?42.4 ± 1.2, and ‐49.7 ± 0.8 kcal/mol, respectively. The structural and thermochemical data presented for CH₃SCH₂CHO, CH₃CH₂SCHO, and CH₃SC(═O)CH₃ and their radicals are of value in understanding the mechanism and kinetics of methyl ethyl sulfide oxidation under varied temperatures and pressures. Group additivity values are developed for estimating properties of structurally similar, larger sulfur‐containing compounds.     

Red,green and infrared three-wavelength lasers generated from LD side-pumped Nd3+:YAG crystal

To obtain 1064 nm/532 nm/660 nm three wavelength lasers operating simultaneously or singly, a novel LD side-pumped Nd³⁺:YAG laser system with acousto-optic Q-switched and nonlinear frequency conversion technologies was investigated. When the three wavelength lasers output singly and the Pumping power was 103 W, 1064 nm laser was 14.5 W and the green and red lasers reached 4.7 W and 1.6 W, respectively, at the repetition rate of 10.5 kHz and 11.5 kHz. When they worked simultaneously, the red, green and infrared lasers were obtained with the output power distribution of 1.0 W at 660 nm, 4.3 W at 532 nm and 10.1 W at 1064 nm, and the instability was less than 2% within 3 h.     

Optical pumping by CO2 and N2O lasers: New cw FIR emissions in vinyl cyanide

A systematical study of optical pumping by CO₂ and N₂O lasers using a FIR metallic waveguide has been undertaken in vinyl cyanide. 97 new FIR laser lines are reported in the wavelength range 400 m–1,5 mm.Unité associée au CNRS (UA 836).     

Spectroscopic features of Pr, Nd, Sm and Er ions in Li2O-MO (Nb2O5, MoO3 and WO3)-B2O3 glass systems

Li₂O-MO (Nb₂O₅, MoO₃ and WO₃)-B₂O₃ glasses doped with four rare earth ions, viz., Pr³⁺, Nd³⁺, Sm³⁺ and Er³⁺ (of 1.0 mol% each) were prepared. The glasses were characterized by X-ray diffraction, differential scanning calorimetry, ESR, optical absorption and photoluminescence spectra. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory, various radiative properties like transition probability A, branching ratio β_r, the radiative life time τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of the data indicated high non-radiative losses in Nb₂O₅ mixed glasses.     

New far-infrared laser lines from CH3Cl and CH3Br optically pumped with a continuously tunable high pressure CO2 laser

In this paper we report on the detection of new far-infrared laser lines from CH₃Cl and CH₃Br optically pumped with a continuously tunable high pressure CO₂ laser. We found 80 new lines for CH₃Cl and 9 new lines for CH₃Br in the frequency region between 16 cm^–1 and 41 cm^–1, all due to stimulated Raman scattering. For the Raman gain regions bandwidths up to about 700 MHz were found. We also observed high intensity short far-infrared laser pulses of durations in the nanosecond regime.Permanent address: Physics Department, State Pedagogical University, SU-119435 Moscow, USSR     

Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate,CF3CO2CH2CH3

The molecular structure and conformational properties of ethyl trifluoroacetate, CF₃CO₂CH₂CH₃, were determined in the gas phase by electron diffraction, and vibrational spectroscopy (IR and Raman). The experimental investigations were supplemented by ab initio (MP2) and DFT quantum chemical calculations at different levels of theory. Experimental and theoretical methods result in two structures with C_s (anti–anti) and C₁ (anti–gauche) symmetries, the former being slightly more stable than the latter. The electron‐diffraction data are best fitted with a mixture of 56% anti–gauche and 44% anti–anti conformers. The conformational preference was also studied using the total energy scheme, and the natural bond orbital scheme. Also, the infrared spectra of CF₃CO₂CH₂CH₃ are reported for the gas, liquid and solid states, as is the Raman spectrum of the liquid. The comparison of experimental averaged IR spectra of C_s and C₁ conformers provides evidence for the predicted conformations in the IR spectra. Harmonic vibrational wavenumbers and scaled force fields have been calculated for both conformers. Copyright © 2009 John Wiley & Sons, Ltd.     

New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu for PDP applications

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) characteristics of Eu³⁺ ion doped borate phosphors; BaZr(BO₃)₂:Eu³⁺ and SrAl₂B₂O₇:Eu³⁺ are studied. The excitation spectra show strong absorption in the VUV region with the absorption band edge at ca. 200 nm for BaZr(BO₃)₂:Eu³⁺ and 183 nm for SrAl₂B₂O₇:Eu³⁺, respectively, which ensures the efficient absorption of the Xe plasma emission lines. In BaZr(BO₃)₂:Eu³⁺, the charge transfer band of Eu³⁺ does not appear strongly in the excitation spectrum, which can be enhanced by co-doping Al³⁺ ion into the BaZr(BO₃)₂ lattices. The luminescence intensity of BaZr(BO₃)₂:Eu³⁺ is also increased by Al³⁺ incorporation into the lattices. The PL spectra show the strongest emission at 615 nm corresponding to the electric dipole ⁵D₀→⁷F₂ transition of Eu³⁺ in both BaZr(BO₃)₂ and SrAl₂B₂O₇, similar to that in YAl₃(BO₃)₄, which results in a good color purity for display applications.     

Optically-Pumped Far-Infrared Laser Lines of Methanol Isotopomers: 12CH3OH, 12CH3OD, and 12CH2DOH

Twenty-seven new far-infrared laser lines from the isotopomers of methanol: ¹²CD₃OH, ¹²CH₃OD, and ¹²CH₂DOH, were obtained by optically-pumping the molecules with an efficient cw CO₂ laser. The CO₂ laser provided pumping from regular, sequence, and hot-band CO₂ laser transitions. The 2-m long far-infrared cavity was a metal-dielectric waveguide closed by two, flat end mirrors. Several short-wavelength (below 100 m) lines were observed. The frequencies of 28 laser lines observed in this cavity (including new lines and already known lines) were measured with a fractional uncertainty limited by the fractional resetability of the far-infrared laser cavity, of 2 parts in 10⁷.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.