Vibrational and Rotational Spectroscopy of 13CD3OD

We have used Fourier Transform spectral data on the C-O stretching mode of ¹³CD₃OD in order to perform a vibro-rotational analysis for this molecule. We have estimated a few molecular parameters of the ground and C-O stretching vibrational modes. Based on these parameters, and by using the Kwan-Dennison model, we propose assignments for a number of far-infrared laser transitions of ¹³CD₃OD.     

Infrared optoacoustic spectroscopy of13CD3OD around the 10R and 10P CO2 laser lines

In this work we present the results of an investigation about Doppler limited infrared absorbing transitions of the C-O stretching vibrational mode of¹³CD₃OD by means of optoacoustic detection. This technique is an alternative, more sensitive and of higher resolution than the Fourier transform spectroscopy which is applied to this methanol isotopomer, due to the contamination problem associated with the fast exchange of OD by OH in the molecule. Using a waveguide CO₂ laser of 290 MHz tunability on each line we were able to observe 69 absorptions, most of then of large offset. The data will be useful in theoretical analysis of this sample, as well as a guide in the search for new FIR laser lines.     

Infrared and far-infrared spectroscopy of CH3OH: TeraHertz laser lines and assignments

We use a ¹³CO₂ laser as optical pumping source to search for new THz laser lines generated from ¹³CH₃OH. Nineteen new THz laser lines (also identified as far-infrared, FIR) ranging from 42.3 μm (7.1 THz) to 717.7 μm (0.42 THz) are reported. They are characterized in wavelength, offset, relative polarization, relative intensity, and optimum working pressure. We have assigned eight laser lines to specific rotational energy levels in the excited state associated with the C-O stretching mode.     

Infrared diode laser spectroscopy of FCO: The ν1 and ν2 bands

The ν₁ (CO stretching) and ν₂ (CF stretching) bands of the FCO radical were observed with Doppler-limited resolution by an infrared diode laser spectrometer with Zeeman and source modulation. The FCO radical was generated by a 60-Hz discharge in one of the following three gas mixtures: O₂ + C₂F₄, CO + SF₆, and CO + C₂F₄, all diluted with He. The observed spectra were analyzed to determine the rotational constants, the centrifugal distortion constants, and the spin-rotation interaction constants. The band origins, 1861.6372(1) and 1026.1283(1) cm^?1 [with standard errors in parentheses], which were obtained, were found to agree well with matrix data, 1857 and 1023 cm^?1, respectively. The assignment of the observed spectra to the FCO radical was further supported by observing the ν₁ band of F¹³CO, which was obtained from ¹³CO and SF₆. The molecular structure and the force field of FCO are briefly discussed by using molecular constants obtained from the observed spectra.     

Spectroscopy of the excited C-O stretching Q branch of 13CD3OH: Measurement and assignment of new FIR laser lines

The Q branch of the C-O stretching fundamental band of ¹³CD₃OH has been investigated. Starting from a high resolution (4 × 10⁻³cm⁻¹) infrared Fourier transform spectrum and using a waveguide CO₂ laser of 300 MHz tunability and an acoustooptic modulator for an extension of ±90 MHz, 31 new FIR laser lines have been observed. The related absorptions have been measured by means of optoacoustic detection. The frequency of one new FIR laser line was also measured. Eight tentative assignments are proposed for the IR absorption and FIR laser emissions.     

The diode laser spectrum of the ν2 band of 14ND3 and 15ND3

The spectra of the ν₂ bands of ¹⁴ND₃ and ¹⁵ND₃ were measured under Doppler-limited resolution with a diode laser spectrometer in order to resolve the K structure of the sR(J, K) and aR(J, K) multiplets. By a simultaneous least-squares analysis of these data, the Fourier spectra of the ν₂ band measured by Jones [J. Mol. Spectrosc.74, 409 (1979)], and the ground-state microwave transitions, sets of improved ν₂-band parameters were obtained, including the sextic centrifugal distortion coefficients.     

Infrared spectra and stability of CO and H2O sorption over Ag-exchanged ZSM-5 zeolite: DFT study

The infrared spectra and stability of CO and H₂O sorption over Ag-exchanged ZSM-5 zeolite were investigated by using density function theory (DFT). The changes of NBO charge show that the electron transfers from CO molecule to the Ag⁺ cation to form an σ-bond, and it accompanies by the back donation of d-electrons from Ag⁺ cation to the CO (π*) orbital as one and two CO molecules are adsorbed on Ag-ZSM-5. The free energy changes ΔG, −5.55 kcal/mol and 6.52 kcal/mol for one and two CO molecules, illustrate that the Ag⁺(CO)₂ complex is unstable at the room temperature. The vibration frequency of C-O stretching of one CO molecule bonded to Ag⁺ ion at 2211 cm⁻¹ is in good agreement with the experimental results. The calculated C-O symmetric and antisymmetric stretching frequencies in the Ag⁺(CO)₂ complex shift to 2231 cm⁻¹ and 2205 cm⁻¹ when the second CO molecule is adsorbed. The calculated C-O stretching frequency in CO-Ag-ZSM-5-H₂O complex shifts to 2199 cm⁻¹, the symmetric and antisymmetric O-H stretching frequencies are 3390 cm⁻¹ and 3869 cm⁻¹, respectively. The Gibbs free energy change (ΔGH₂O) is −6.58 kcal/mol as a H₂O molecule is adsorbed on CO-Ag-ZSM-5 complex at 298 K. The results show that CO-Ag-ZSM-5-H₂O complex is more stable at room temperature.     

Large offset far infrared laser lines generation from the C-O stretching Q-branch of 13CD3OD

2 laser of wide tunability to pump ¹³CD₃OD we could observe 10 new far infrared laser lines ranging from 109 μm to 472 μm. The lines were generated by pumping infrared absorbing transitions of large offset appertaining to the C-O stretching Q-branch. All lines were characterised in wavelength, polarisation, optimum pressure of operation and precise offset measurements. Received: 17 September 1996/Revised version: 18 November 1996     

The infrared spectrum of the ν1 and ν4 bands of 28SiH3D

The spectrum of the ν₁ and ν₄ SiH stretching bands of ²⁸SiH₃D have been recorded and analyzed. The degenerate stretching mode is at 2188.504 cm^?1, only 1.103 cm^?1 above the symmetric stretching mode. Several accidental and essential resonances affect these bands but all have been successfully analyzed by diagnolization of the secular determinant complete through the second order of the transformed Hamiltonian. One accidental resonance leads to a number of forbidden transitions through which a value of the rotational constant A₀ has been obtained.     

Photophysical studies of uranyl complexes 5. Luminescence spectrum of K4UO2(CO3)3

The photoluminescence of K₄UO₂(CO₃)₃ has been studied under conditions of high resolution at cryogenic temperatures. The origin corresponding to the pure electronic transition was located at 4774 Å (20945 cm^-1), and it was found that the totally symmetric uranyl stretching mode was coupled to this transition. A progression of four band systems thus resulted, and from an examination of the energies of corresponding peaks in each system, a value of 813 cm^-1 for the U-O stretching mode was determined. Two lattice modes (34 and 80 cm^-1) and two molecular vibrational modes (205 and 276 cm^-1) were also found to couple with the pure electronic transition, thus yielding approximately 15 major peaks in each band system. The 205 cm^-1 vibration corresponded to a CO^2-₃ vibration, while the 276 cm^-1 vibration was a UO²⁺₂ deformation. The low values obtained for the force constant and totally symmetric stretching frequency of the U-O bond suggested that in UO₂(CO)^4-₃, the uranium atom is bound in a complex species that may be considered as an intermediate between that of a uranyl (UO²⁺₂) and a uranate (UO^10-₈) ion.     

The ν2 band of 14NH3: A calibration standard with better than 1 × 10−4 cm−1 precision

The Fourier transform spectra and the diode laser spectra of the ν₂ band of ¹⁴NH₃ have been measured with 0.005 and 0.002 cm^?1 resolution, respectively. A simultaneous least squares analysis has been carried out of these data together with the microwave, submillimeterwave, diode-laser heterodyne, and infrared-microwave two-photon transition frequencies between the ground and the ν₂ inversion-rotation levels. A theory of the Δk = ±3n interactions in the ground and ν₂ excited states of ammonia (?. Urban, V. ?pirko, D. Papou?ek, J. Kauppinen, S.P. Belov, L. I. Gershtein, and A. F. Krupnov, J. Mol. Spectrosc.84, 288–304 (1981)) has been used in the analysis. The “smoothed” values of the ν₂ band wavenumbers can be used for calibration purposes with better than 1 × 10^?4 cm^?1 precision. On the basis of these results, a critical evaluation has been carried out of several experimental techniques of very high resolution infrared spectroscopy.     

High resolution fourier transform spectrum of PD3 in the region of the stretching overtone bands 2ν1 and ν1+ν3

The infrared spectrum of the PD₃ molecule has been measured in the region of the first stretching overtone bands on a Fourier transform spectrometer with a resolution of 0.0068 cm⁻¹ and analyzed for the first time. More than 800 transitions with J^max=15 have been assigned to the bands 2ν₁ and ν₁+ν₃. An effective Hamiltonian was used which takes into account both the presence of resonance interactions between the states (2 0 0 0) and (1 0 1 0), and interactions of these with the third stretching vibrational state of the v=2 polyad, (0 0 2 0). A set of 44 spectroscopic parameters is obtained from the fit. This reproduces the 305 initial “experimental” upper rovibrational energies with an rms=0.0015 cm⁻¹.     

New far infrared laser lines in optically pumped CD3F

Summary Using a high pressure CO₂-laser we have studied laser action in¹²CD₃F stimulated by R-branch pumping. We used an arrangement with low-feedback mirrors as suitable for Raman laser action. However, no Raman laser action has been observed in¹²CD₃F though similar experimental conditions were met as for¹²CH₃F and¹³CH₃F. The reason for the different behavior of the gases is not yet clear.Instead of Raman laser action we found 15 FIR resonant laser lines with 13 of them unknown up to now in the frequency range from 50 cm^–1 to 68 cm^–1. We reached FIR pulse energies up to 900 J, corresponding to a photon conversion efficiency of 12%. For our arrangement the optimum operation pressure varied from 40 torr at low J values (J=36) to 70 torr at high J values (J=49).     

Doppler-free optoacoustic spectroscopy of O-18 methanol

The Doppler-free optoacoustic spectrum of the oxygen-18 species of methanol has been investigated with a CO₂ laser. Seventeen coincidences have been found between infrared absorptions of CH¹⁸₃OH and CO₂ laser lines. The strongest feature seen, pumped by the 10R(20) CO₂ laser line, has two plausible alternative identifications, determined from a parallel high-resolution spectroscopic study of the C-O stretching band. Further experimental tests are suggested to resolve the assignment, and predicted far-infrared laser frequencies are given for the two possibilities.     

R branch tuning characteristics of the13CH3F Raman FIR laser

Summary We described a¹³CH₃F Raman laser pumped by a grating tuned 20 atmospheres CO₂ laser. The emission characteristics of the¹³CH₃F laser extends from 14 cm^–1–35 cm^–1 and from 49 cm^–1–72 cm^–1; about 65% of these frequency ranges can be covered with tunable radiation. The characteristics shows a strong dependence on the rotaional quantum numbers of the states involved in the Raman laser transitions and, within each tuning interval, on the frequency offset with respect to the frequencies of resonant transitions. We obtained, at 51 cm^–1, a maximum FIR laser pulse energy of about 800 J (at a pump energy of 200 mJ), corresponding to a photon conversion of about 8%. In some cases we have observed simultaneous emission at a Raman and a cascade frequency. In addition, FIR emission power dependence on¹³CH₃F gas pressure and pump pulse power were investigated for different J quantum numbers.     

Upconversion-pumped population kinetics for4I13/2 and4I11/2 laser states of Er3+ ion in several host crystals

Population kinetics of the upper⁴I_11/2 and lower⁴I_13/2 laser states of the Er³⁺ ion were studied experimentally and theoretically in (Er)BaY₂F₈, (Er)YLF, (Er)YSGG, (Er)CaF₂ and (Er)YALO. Fluorescence from these states to the⁴I_15/2 ground state was excited through upconversion simultaneously with the⁴I_11/2 ⁴I_13/2 lasing using 1.53 µm radiation from an erbium : glass laser for optical pumping. Lifetimes of both states are altered during lasing by co-operative energy transfer processes: the lifetime of the lower state ₁ is shortened and that of the upper state ₂ increased with the resultant ratio ₂/₁>1. After lasing the lifetime ratio returns to the normal value ₂/₁ <1; that=" is,=" one=" obtained=" under=" weak=" ultraviolet=" excitation.=" kinetic=" rate=" equations=" for=" the=" population=" density=" functions=" for=" both=" laser=" states=" were=" set=" up=" and=" solved=" by=" approximation=" in=" three=" time=" domains.=" it=" was=" assumed=" that=" only=" one=" co-operative=" energy=" transfer=" process=" operates=" in=" the=" laser=" crystals=" and=" determines=" the=" population=" inversion=" kinetics.=" consistency=" relationships=" for=" comparison=" of=" the=" theoretical=" results=" with=" the=" experiment=" were=" developed.=" only=">₂F₈ spectral features showed close agreement with theory, resulting in a high score of 94% for the overall correlation in the consistency test, whereas all other crystals scored <50%. as=" a=" result=" of=" this=" high=" correlation,=" a=" close=" match=" between=" theoretical=" and=" experimental=" population=" decay=" curves=" was=" shown=" for=">₂F₈. Most probably, more than one energy transfer process shapes the decay curves and determines the population inversion kinetics for the other laser crystals. (Er)YALO showed little lifetime change for the laser states, apparently due to inefficient co-operative energy transfer processes. As a result it probably lased in a self-terminating short-pulse mode.     

Rotational analysis of the ν1, 2ν1 and 5ν1 stretching bands of HGeD3

The high-resolution spectrum of the ν₁=5 stretching overtone of gaseous H⁷⁰GeD₃ has been recorded by an intracavity laser absorption spectrometer based on a vertical external cavity surface emitting laser (VECSEL). The rotational structure of the excited state at 9874.605 cm⁻¹ was found weakly perturbed by unidentified interaction with dark states. Finally, of the 313 lines rotationally assigned, 239 lines were found unperturbed and could be reproduced with a root-mean-square (rms) deviation of 0.012 cm⁻¹. The retrieved set of rotational parameters agrees with the values extrapolated from the previously studied ν₁=6-8 stretching overtones. High-resolution FTIR spectra of the ν₁ and 2ν₁ bands have also been recorded and analyzed. The ν₁=1 level, (ν_eff=2114.15 cm⁻¹) is in anharmonic interaction with a further A₁ symmetry level (ν_eff=2102.39 cm⁻¹). The potential coupling term could be estimated (W_anh=5.6(3) cm⁻¹) and the most probable assignment of the perturber is ν₂+ν₃. Moreover both levels are rotationally perturbed in an irregular fashion. Only a coarse analysis up to J=6 could be performed. The 2ν₁ band reveals irregular perturbations of medium intensity by unknown dark states for almost all K values. Nevertheless the obtained leading rovibrational parameters of the 2ν₁ band for J?6 are in agreement with those of the ν₁=5-8 states.     

CH3I: Isotope shift for 129I in the v6 band

The isotope shift in the v₆ band of CH₃I has been measured with high resolution for the radioisotope ¹²⁹I (half-life = 1.6 × 10⁷ y) with respect to the stable ¹²⁷I, using tunable diode laser spectroscopy. The average shift obtained from 30 transitions, free from interference in the ^RQ(J, 3) and ^RQ(J, 4) branches, amounted to (-0.0135 ± 0.0006) cm^-1. The abundance ratio ¹²⁹I/¹²⁷I in the gas mixture was determined spectroscopically on ^RQ(16, 3) and found to be (0.032 ± 0.003), as compared to a mass-spectrometric analysis of (0.030 ± 0.001). The self and air broadening coefficients measured on ^RR(6, 0) of CH₃¹²⁷I were (32 ± 3) MHz Torr^-1 and (10.4 ± 1.5) MHz Torr^-1 respectively. The line strengths for ^RQ(16, 3) were found to be (2.0 ± 0.2) × 10^-21 cm^-1 mol^-1 cm² for both CH₃¹²⁷I and CH₃¹²⁹I.     

Continuous-wave and Q-switched laser operation of Nd:Gd0.18Y0.82VO4 mixed crystal

Efficient continuous-wave (cw), passively Q-switched, and actively Q-switched laser operations are demonstrated with a mixed vanadate crystal of Nd:Gd_0.18Y_0.82VO₄ under diode pumping. In a cw operation, an output power of 8.25 W is obtained at a maximum available incident pump power (P_in) of 15 W, with a slope efficiency of 56%. Using a Cr⁴⁺:YAG crystal of initial transmission of 62% as the saturable absorber for Q-switching, an average output power of 3.05 W is generated at pulse repetition frequency (PRF) of 16.7 kHz when the laser is pumped with the same maximum P_in. The pulse energy, pulse duration, and peak power are 183.3 μJ, 6.0 ns, and 30.6 kW, respectively. When actively Q-switched by an acousto-optic modulator, the laser produces an average output power of 5.5 W at PRF of 30 kHz with 16.2 W of pump power incident upon the laser crystal. The pulse energy, duration, and peak power are measured to be 183 μJ, 10.5 ns, and 17.5 kW, respectively.     

Analysis of the ν2 and ν4 infrared bands of CD4

The infrared spectrum of totally deuterated methane CD₄ has been recorded between 930 cm^?1 and 1180 cm^?1 under high resolution (0.003 cm^?1). The ν₂ and ν₄ bands of ¹²CD₄ have been reanalyzed on the basis of a complete third-order Hamiltonian including all the coupling terms linking the upper states of the two bands. A set of only 16 self-consistent parameters have been adjusted to fit more than 1650 assigned transitions reaching a maximum upper state J value of 20. The obtained standard deviation is 0.0041 cm^?1. In addition, 171 lines of the ν₄ band of ¹³CD₄ have been assigned. They have been analyzed, in the same dyad scheme, by adjusting 7 parameters of the ν₄ band together with the main ζ₂₄ Coriolis parameter. The obtained standard deviation is only 0.0012 cm^?1.