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.     

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 of CHD2OH Around 10R and 10P CO2 Laser Lines

In this work we present results of an investigation on Doppler limited infrared absorbing transitions of CHD₂OH by optoacoustic detection. It is an alternative and attractive technique to be applied to this methanol isotopomer, in comparison to Fourier transform spectroscopy. Using a waveguide CO₂ laser of 290 MHz tunability on each line, we were able to observe 60 IR absorptions, most of them of large offset. The data will be useful in the theoretical analysis of this molecule, as well as in the generation of far-infrared (FIR) laser radiation in optically pumped molecular lasers.     

Far infrared laser lines produced by methanol and its isotopic species: A review

Methanol (CH₃OH) is considered today one of the most important active media for the generation of laser radiation in the far-infrared (FIR) spectral region. Together with ten of its other isotopic species, it is responsible for the major part of the laser lines generated by the optical pumping technique. Due to the extreme importance of those molecules as laser generators, we understood that there was a necessity of a comprehensive work which would include as much pratical information as possible about each line.Chang et al⁽¹⁾ early recognized methanol as a source of strong FIR laser lines. Since then, more than 100 papers were published containing information about new laser emission. Recently, Moruzzi et al⁽¹¹⁴⁾ presented a review of 575 lines produced by¹²CH₃OH. In the present paper, we have extended the review to the various isotopic modifications of this molecule (namely¹³CH₃OH, CD₃OH,¹³CD₃OH, CD₃OD,¹³CD₃OD, CH₃OD, CH ₃ ¹⁸ OH, CH₂DOH, CH₂DOD and CHD₂OH), a total of nearly 2000 lines with wavelengths ranging from 19µm to 3030µm.     

Spectroscopy of Methanol and Its Application to Optically Pumped THz FIR Lasers

In this paper, we have reviewed the details of experimental and theoretical aspects of the high-resolution molecular spectroscopy of methanol isotopomers. The methods of spectroscopic assignments and analysis have been discussed. The applications of the spectroscopic techniques, particularly of Fourier transform spectroscopy in the field of optically pumped Terra-Hertz Lasers (OPTL) and far infrared (OPFIR) lasers have been discussed. New assignments have been deduced for TEA-CO₂ laser pumped methanol and CW CO₂ pumped ¹³CD₃OD. Stark effect analyses and the determination of accurate dipole moment values have been discussed for CH₃OH, ¹³CH₃OH and CH₃ ¹⁸0H. The importance of high-resolution spectroscopy is also discussed in terms of astrophysical detection. Some recent ongoing astrophysical efforts are outlined. In our laboratory we are in the process of setting up a THz methanol laser for astrophysical applications and search for new coherent monochromatic laser sources.     

A review of optically pumped far-infrared laser lines from methanol isotopes

The technique of optical pumping in polar molecules is the most efficient for Far-Infrared (FIR) laser generation, providing also a versatile and powerful tool for molecular spectroscopy in this spectral region. Methanol (CH₃OH) and its isotopic varieties are the best media for optically pumped FIR laser, with over thousand lines observed, and the most widely used for investigations and applications. In this sense, it is important organize and make available catalogues of FIR laser lines as complete as possible. Since the last critical reviews of 1984 [1] on methanol and its isotopic varieties [2,3,4], over hundred papers have been published dealing with hundreds of new FIR laser lines. In 1992 a review of FIR laser lines from CH₃OH was presented [5]. In this communication we extend this work to the other methanol isotopes, namely CH₃OD, CD₃OH, CD₃OD,¹³CH₃OH,¹³CD₃OH,¹³CD₃OD, CH₃ ¹⁸OH, CH₂DOH, CHD₂OH and CH₂DOD.Work supported by FAPESP, CNPq, FAEP-Brasil, and CNR-Italia     

FIR Laser Lines from CH3OD: A Review

The methanol isotopic species CH₃OD has also proved to be an efficient and powerful medium to generate radiation in the far infrared (FIR) region. After the critical review of 1994, six papers have been published dealing with new FIR laser lines from this molecule. As a consequence of the use of wide tunability waveguide CO₂ lasers as well as a new pulsed CO₂ laser operating at hot and sequential bands, as of optical pumping sources, the total number of the FIR laser lines increased from 122 in 1994 to 227 today. In this communication we present an updated and complete catalogue of FIR laser lines generated from CH₃OD. Information on wavelength, offset, relative polarization, intensity, and optimum operation pressure is generally available.     

FIR laser assignments and frequency predictions for optically pumped13CD3OH by high-resolution Fourier transform spectroscopy

Continued study of the high-resolution Fourier transform spectroscopy (FTS) of the fundamental CO-stretching band of¹³CD₃OH has given additional insight into the far-infrared (FIR) laser emission observed when this molecule is optically pumped by a CO₂ laser. Eleven IR-pump/FIR-laser transition systems are considered. Seven represent completely new assignments, while four have been presented previously but are discussed further with reference to recently reported experimental data. Ten of the assignment schemes have been rigorously checked by forming closed combination loops, and accurate FIR laser wavenumbers have been obtained. The superiority in precision of the FIR laser wavenumbers determined from FTS combination loops over those from traditional wavelength measurements is demonstrated.     

Infrared diode laser spectroscopy

Three types of lasers (double-heterostructure 66 K InAsSb/InAsSbP laser diode, room temperature, multi quantum wells with distributed feedback (MQW with DFB) (GaInAsSb/AlGaAsSb based) diode laser and vertical cavity surface emitting lasers (VCSELs) (GaSb based) have been characterized using Fourier transform emission spectroscopy and compared. The photoacoustic technique was employed to determine the detection limit of formaldehyde (less than 1 ppmV) for the strongest absorption line of the v₃ + v₅ band in the emission region of the GaInAsSb/AlGaAsSb diode laser. The detection limit (less than 10 ppbV) of formaldehyde was achieved in the 2820 cm⁻¹ spectral range in case of InAsSb/InAsSbP laser (fundamental bands of v₁, v₅). Laser sensitive detection (laser absorption together with high resolution Fourier transform infrared technique including direct laser linewidth measurement, infrared photoacoustic detection of neutral molecules (methane, form-aldehyde) is discussed.     

Overtone spectrum and the Fermi resonance of the SiH chromophore in SiHCI3

The Fourier transform and Fourier transform intracavity laser absorption spectra of the gas phase SiHCl₃ molecule were recorded from 1000 cm-¹ up to 13 000 cm-¹. The normal mode analysis is carried out to fit the observed band centres. The reduced Hamiltonian models in terms of normal and curvilinear internal coordinates are used to study the Fermi resonance between the SiH stretching and bending modes and analyse the observed band centres associated with the SiH chromophore. The resonance in the SiH chromophore is found not to be important due to the cancellation of the contributions from the kinetic and the potential coupling terms. Off-diagonal anharmonic constants between the SiH stretching and bending manifold and the molecular frame have been determined. The SiH chromophore vibrational intensities are also reported.     

Associative versus dissociative adsorption of water on Al(100)

The adsorption of water on Al (100) at 100 K has been studied using Fourier transform infrared-reflection absorption spectroscopy (FTIR-RAS), nuclear reaction analysis (NRA) and work function measurements (Δφ). All results are consistent with molecular adsorption, as no evidence was found for other possible dissociation products such as atomic O or D (H) at this temperature. By condensing alternating layers of D₂O and H₂O, it was found that a narrow feature in the _v(OD) (_v(OH)) region of the spectrum at 2720 cm⁻¹ (3700 cm⁻¹) is associated with non-hydrogen bonded OD (OH) groups in water molecules existing at the ice-vacuum interface. Surface hydroxyl groups resulting from dissociative adsorption exhibit a broader O-D stretch at 2760 cm⁻¹.     

Thermal release of trapped deuterium from silica injected by 80-keV D+ ion implantation and RF D2 plasma

When silica is irradiated by 80-keV D⁺ ions or RF plasma of D₂ gas, deuterium is trapped in the silica forming Si-OD bonds. The deuterium, trapped as OD bonds, is desorbed from the silica upon heating to form some release products. The thermal detrapping process corresponds to decrease of OD bonds and was studied by measurement of infrared Fourier transform spectroscopy (FTIR). The release products HDO, D₂O, HD, and D₂ were measured by quadrupole mass spectroscopy (QMS). The detrapping and release processes of trapped deuterium were studied by simultaneous measurement of FTIR and QMS. Since the release spectra of HDO, D₂O, HD, and/or D₂ correspond to the decrease spectra of OD bonds, these release products are formed by thermal decomposition of OD bonds. The formation of water (HDO, D₂O) and hydrogen (HD, D₂) depends upon concentration of pre-existing OH bonds and deuterium injection methods (80-keV D⁺ implantation or RF D₂ plasma irradiation).     

Multiple submillimeter emissions of difluoromethane pumped by cw 9R(6) laser line of 12C16O2

Pumped by the 9R(6) ¹²C¹⁶O₂ laser lines, CH₂F₂ produces five SMM emissions. Levels involved in this process are identified with the help of a Fourier transform spectrum. Among these emissions we find cascade and intervibrational transitions allowed by Coriolis resonance between v₉ and v₃.     

A build-up cavity for Fourier transform emission experiments

We have recorded electronic spectra of some diatomic species (I₂, K₂, and NaK), to illustrate the potential power of the combination of two high resolution techniques: intra-cavity laser induced fluorescence (ICLIF) and Fourier transform (FT) spectroscopy. Active and passive optical cavities have been used, working with visible continuous wave (cw) laser sources. The active cavity is a modified commercial ring dye laser, allowing for a sample up to 25 cm in length. Dispersed fluorescence spectra recorded on a Bomem Fourier transform spectrometer showed a signal enhancement of about 10 when a molecular source was placed within the resonator. The system was tested with a heatpipe source, producing alkali metal vapour at about 300 °C. These experiments illustrate enhanced cascade excitation mechanisms in K₂; the highest vibrational levels of the electronic ground state of K₂ can be observed with surprising ease. The increase in available power within the cavity has also led to the observation of fluorescence in NaK excited by a two-photon transition (Q (66) 6¹Σ⁺ ← X¹Σ⁺ transition). Spatial limitations have driven us to build a more versatile ring cavity able to accommodate larger sources. This broad-band (590-650 nm) build-up cavity is locked by a Hänsch-Couillaud servo-loop to an input laser of (instantaneous) bandwidth ∼1 MHz. Power enhancement factors of around 30 have been obtained with a 2.6% input coupler. The performance of the build-up cavity has been tested by recording FT spectra of intra-cavity laser induced fluorescence of iodine. The technique clearly has useful applications for weakly absorbing species, or for those whose electronic states are inaccessible to single-photon absorption techniques. This paper describes the arrangement we have used, highlighting some of the advantages and describing some of the particular difficulties we have encountered.     

IR and FIR spectroscopy of 13CD3OH around the 10P(22) and 10P(24) CO2 laser lines: New FIR laser emissions,frequency measurements and assignments

By using high resolution infrared Fourier transform data on ¹³CD₃OH and the 10P(22) and 10P(24) lines of a waveguide CO₂ laser to optically pump this methanol isotope, eight new FIR laser lines were observed. The frequencies of five laser lines were directly measured by heterodyne detection with already known laser lines. Particularly interesting are the lines pumped by the 10P(24) line, since a triade of emissions could be completely assigned.     

Laser diode photoacoustic and FTIR laser spectroscopy of formaldehyde in the 2.3 μm and 3.5 μm spectral range

The room temperature operating GaInAsSb/AlGaAsSb based diode laser and 66 K InAsSb/InAsSbP laser diode both operating in spectral range of formaldehyde absorption 4350-4361 cm⁻¹ and 2821-2823 cm⁻¹ have been characterized and compared. Very precise arrangement of laser absorption together with high resolution Fourier transform technique was tested. The photoacoustic technique was employed to determine the detection limit of formaldehyde (less than 1 ppmV) diluted by nitrogen for the strongest absorption line of the ν₃ + ν₅ band in the emission region of the GaInAsSb/AlGaAsSb diode laser. The detection limit (less than 10 ppbV) of formaldehyde was achieved in the 2820 cm⁻¹ spectral range in case of InAsSb/InAsSbP laser (fundamental bands of ν₁, ν₅)_.     

Vibration-internal rotation-rotation Hamiltonian of an asymmetric top molecule with C3v internal rotor

An expression for the kinetic energy part of the vibration-torsion-rotation Hamiltonian of an asymmetric top molecule containing a C_3v internal rotor has been derived. The terms for various interactions in the molecule, viz. Coriolis interaction between rotation (both overall and internal rotation) and vibration, centrifugal distortion and anharmonicity of molecular vibrations induced by the internal, and overall rotation of the molecule, have been formulated. For a planar molecule with C_s symmetry we have obtained the vibrationally averaged rotation-internal rotation Hamiltonian. Diagonalization of this Hamiltonian for a particular vibrational state will yield the rotation-internal rotation energy levels and hence the transition frequencies. These data will be useful for analysis of high-resolution infrared spectra obtained by laser or Fourier transform spectroscopy of nonrigid molecules with internal rotor. We also present a set of quartic centrifugal distortion coefficients associated with rotation and internal rotation. These data will be helpful for evaluation of vibrational potential constants of the orthorhombic asymmetric top molecules.     

Laser Lines and Frequency Measurements of Fully Deuterated Isotopomers of Methanol

Fully deuterated isotopomers of methanol (¹²CD₃OD and ¹³CD₃OD) were optically pumped with a CO₂ laser. Five new far-infrared laser lines were discovered in ¹²CD₃OD and 25 in ¹³CD₃OD in the range 43.697 to 719.426 m. The frequencies of these new and some previously reported laser lines, the pump offset, the relative polarization, the relative intensity, and the optimum pressure of operation were measured.     

Atlas of the O-18 Methanol THZ Fourier Spectrum

In this paper, an atlas of the assigned high-resolution Fourier transform spectra in the range 30-133 cm^-l, corresponding far-infrared torsion-rotation band of O-18 methanol in the vibrational ground state, is presented. The estimated accuracy of the lines is ±0004 cm^-l. This will be of great assistance with our assignments of optically-pumped FIR laser emission in CH₃ ¹⁸0H, in providing FIR data for checking the identification of the IR-pump/FIR-laser transition systems through combination loop relations.     

Fourier transform microwave spectroscopy of aluminum hydrosulfide, AlSH

Pure rotational transitions of three isotopic species of aluminum hydrosulfide, AlSH, have been measured with a cavity pulsed jet Fourier transform microwave spectrometer. AlSH was prepared by the reaction of laser ablated Al metal with H₂S, and was stabilized in pulsed supersonic free jets of Ar. For each species the transition 1₀₁-0₀₀ was measured; hyperfine structure due to the nuclear spin of ²⁷Al was observed for the first time and analyzed. For Al³²SH and Al³²SD, the rotational constants are in excellent agreement with published values. For the third species, Al³⁴SH, this is the first observation, and its rotational constants are consistent with the published geometry. Information on the electronic structure of the molecule has been obtained using the ²⁷Al nuclear quadrupole coupling constants and nuclear spin-rotation constants. The latter have been used to evaluate ²⁷Al NMR shielding parameters, which are compared with those of other ²⁷Al compounds. These shieldings have been found to be in excellent agreement with theoretical predictions. The results should also help facilitate astrophysical searches for the molecule.