New FIR laser lines from optically pumped C2H3F, C2H3Cl, C2H3Br, C2H3CN, C2H5F, CH2CF2, HCOOH and CH3Br

Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C₂H₃F, C₂H₃Cl, C₂H₃Br, C₂H₅F, C₂H₃CN, CH₂CF₂, HCOOH and CH₃Br with a CO₂ laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.     

RESONANCE-ENHANCED MULTIPHOTON IONIZATION SPECTRA OF THE HALOGEN ATOMS

The resonance-enhanced multiphoton ionization (REMPI) spectra of atomic chlorine and bromine in the range of 230-245 nm and 250-285 nm were obtained by using REMPI and time of flight (TOF) techniques. There are twenty -six lines for Cl and twenty-three for Br in the spectra, among which five transitions of Cl and four of Br are observed for the first time. These lines are due to transitions from the Cl(3p ²P⁰_3/2, ²P⁰_1/2) and Br(4p²P⁰_3/2, ²P⁰_1/2) states to upper states induced by two-photon excitation. It is found that the Stark shift of different excited states are almost the same, and they are independent of the S, L, and J quantum numbers of the excited state.     

Pulsed laser deposition of amorphous carbon nitride thin films and their electrical properties

Amorphous carbon nitride thin films were deposited by pulsed laser deposition combined with a nitrogen rf radical beam source. A structural characterization of the deposited films was performed using X-ray photoelectron and Raman-scattering spectroscopy. The Raman spectra showed that the dominant hybridization state of carbon atoms in the deposited film is sp². N 1s electron spectra were deconvoluted into three components, N bonded to pyridine-like N and/or N-sp³C (N1), substitutional N in graphite (N2), and N-O and/or N-N (N3). The proportion of N1 increased with increasing N/C atomic ratio in the film. The electrical conductivity at room temperature decreased and the Tauc optical band gap increased with increasing N/C atomic ratio. The temperature dependence of the electrical conductivity indicated that electronic conduction occurred by variable range hopping between electron localized states. The decrease in electrical conductivity with increasing N/C atomic ratio was caused by a strong electron localization due to the increased proportion of N1. PACS 81.05.Uw; 81-15.Fg; 73.61.Jc     

New cw FIR laser lines from optically pumped silyl fluoride (SiH3F)

FIR laser action has been observed for the first time in a molecule containing silicon: silyl fluoride, SiH₃F. Eleven new cw optically pumped lines between 187 and 1014m were detected from both open resonator and waveguide structures. Although the chlorine analogue, SiH₃Cl, showed strong absorption at every CO₂ laser frequency no FIR laser emission was detected at the pump powers available.     

Continuous laser emission from sodium atoms by collision assisted two-step excitation

Continuous laser oscillation on different lines in the spectral range of 1.85 to 3.41 m, corresponding to transitions between higher lying atomic sodium levels, has been obtained by optical excitation of sodium vapor with Rhodamine 6G dye-laser radiation, tuned either around the 3p–4d resonance ( 568 nm) or the 3p–5s resonance ( 615 nm). The pump mechanism consists of an atomic two-step excitation as well as an excitation of diatomic sodium molecules and subsequent molecular-atomic collisional energy transfer. Laser operation with low threshold pump power (<10 mW) and large pump laser detuning (500 GHz) has been observed.     

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     

Optically-Pumped Far-Infrared Laser Lines in Hydrazine, Methanol, Heavy Water, and Ammonia: New Laser Lines and Frequency Measurements

A far-infrared laser cavity designed to favor short-wavelength laser lines was used to generate optically-pumped far-infrared laser radiation. New far-infrared laser lines were discovered in hydrazine, heavy water, ammonia, and several short-wavelength lines previously discovered in methanol were observed. Wavelength, frequency, and relative intensity measurements were performed on laser lines in the wavelength range 42.4 to 253.7 m. Each far-infrared frequency measurement was obtained by mixing the far-infrared radiation with radiation from two reference CO₂ lasers and from a microwave synthesizer in a metal-insulator-metal diode. The pump laser was a high-Q Fabry Perot resonator oscillating on 275 grating-selected laser lines including regular, sequence, and hot band lines.     

A hollow cathode bismuth ion laser

cw laser oscillations of Bi II at 680.9, 660.0, and 571.9 nm have been achieved for the first time by using a bismuth hollow cathode discharge. In addition, laser oscillations of Bi I at 1.1711 m in the afterglow were observed. The ionic laser lines are excited by Penning ionization. The atomic line is produced by recombination of the bismuth ions and lowenergy electrons in the afterglow.     

Measurement of isotope shifts,fine and hyperfine structure splittings of the lithium D lines

The lithium D lines were studied using a diode laser that was frequency modulated by an electro-optic modulator, to excite an atomic beam. The transmission of part of the laser beam through an etalon was monitored to correct for the nonlinearity of the laser scan. The results for the ^6,7Li 2 S _1/2 and 2 P _1/2 hyperfine splittings agree very well with the best existing data while those for the D1 isotope shift and ^6,7Li fine structure splittings disagree significantly from data obtained by a previous laser atomic beam experiment. Our result for the D1 isotope shift is very close to the latest value computed using Hylleraas variational theory. Received 8 April 2002 / Received in final form 26 June 2002 Published online 21 January 2003 RID="a" ID="a"e-mail: wvw@yorku.ca     

A Mössbauer investigation of complexes of tin tetrahalides with ambidentate Lewis bases containing nitrogen,sulphur and oxygen

A series of 1 : 1 complexes was prepared with SnX₄ (X=Cl, Br, I) and the Lewis bases 2-mercaptobenzothiazole, 2-mercapto-1-methylimidazole, 2-aminothiazole, 2-acetylpyridine, and 2,2-bis(pyridyl)ketone. The latter two ligands yielded bidentate, N, O-bonded hexacoordinate complexes, whereas the other ligands produced monodentate, N-bonded pentaccoordinate species, as suggested by Mössbauer parameters, which correlate quite well with the IR spectroscopy data.     

New cw fir laser emissions from CO2 laser-pumped vinyl bromide

47 new cw far-infrared laser lines with wavelenths between 453 and 2356 m have been obtained by optically pumping vinyl bromide (C₂H₃Br) by a CO₂ laser. A significant portion of these lines has wavelengths longer than 750 m.     

Structural and electronic properties of matlockite MFX (MSr, Ba, Pb; XCl, Br, I) compounds

First-principles calculations have been used to study the structural and electronic properties of technologically important matlockite compounds MFX (MBa, Sr, Pb; XCl, Br, I) using a full potential linearized augmented plane-wave method within density functional theory. We used the local density approximation and the generalized gradient approximation, as well as the Engel-Vosko's GGA formalism to find the band gap and the partial density of states at equilibrium volume. We also optimized internal parameters by relaxing the atomic positions in the force directions. The calculated total energy allowed us to investigate several structural properties in particular the equilibrium lattice constants a and c, c/a ratio, bulk modulus, pressure derivative of the bulk modulus, cohesive energy, interatomic distances, interlayer distances along c axis and the angles between different atomic bonds. We calculated the valence charge density at the equilibrium volume for BaFCl and PbFCl and concluded that the bonding nature in these compounds is mainly ionic. Results are discussed and compared with experimental and other theoretical data.     

Spectral investigation of cw rf-pumped atomic Xe laser with a slab geometry

A radiofrequency excited atomic Xe slab laser with an active volume of 2 × 10 × 300 mm³ using a quartz envelope containing the laser-gas mixture shows a stable cw performance with an output power of almost 1 W. The free-running system oscillates, depending on gas composition and density, on several lines between 1.73 and 3.51 m. Line competition phenomena are observed. Single-line oscillation yields more than 500 mW.     

An Ab Initio Study of the Structural and Electronic Properties of the Low-Defect TiC(110) Surface Simulating Oxygen Adsorption after Exposure to Laser Plasma

An ab initio simulation of the adsorption of atomic oxygen on the low-defect titanium carbide (110) surface reconstructed by laser radiation was performed. The relaxed atomic structures of the (110) surface of the O/Ti _x C _y system with Ti and C vacancies observed during the thermal treatment were studied in terms of the density functional theory. DFT calculations of their structural, thermodynamic, and electronic properties were performed. The bond lengths and adsorption energies were determined for various reconstructions of the atomic structure of the O/Ti _x C _y (110) surface. The effects of the oxygen adatom on the band and electronic spectra of the O/Ti _x C _y (110) surface were studied. The effective charges on the titanium and carbon atoms surrounding the oxygen atom in various reconstructions were determined. The charge transfer from titanium to oxygen and carbon atoms was found, which is determined by the reconstruction of the local atomic and electronic structures and correlates with chemisorption processes. The potential mechanisms of laser nanostructuring of the titanium carbide surface were suggested.     

Optoacoustic Laser Stark spectroscopy and FIR laser action on CH3Br using a waveguide CO2 laser

The optoacoustic spectrum of CH₃Br around 10 m band lines of a tunable cw waveguide CO₂ laser is investigated. Several new infrared absorptions are observed and most of the correspond ing molecular transitions are assigned. Far infra red laser action is reported by pumping with the same CO₂ laser: pump offsets are given using the Transferred Lambs dip (TLD) technique. A new FIR laser emission is obtained and assigned. An optoacoustic Laser Stark spectroscopy technique is used to investigate off resonance infrared tran sitions.     

Chemisorption of halogens on silver a critical comparison of results from photqemission and thermal desorption spectroscopy

Conflicting thermal desorption (TDS) results from submonolayer coverages of atomic Cl, Br or I on Ag(100), Ag(110) or Ag(111) stimulated us to check for the possible influence of different sample preparation procedures. We present experimental evidence, that a combined approach using TDS and angle-resolved ultraviolet photoemission may help to distinguish between better and worse surface preparation. We present detailed new results for the Cl/Ag(110) system. From our observations we conclude that all three halogens listed above give one and only one TDS peak in the submonolayer regime and show very similar adsorption/desorption-characteristics. This fact removes the apparent contradictions reported in the literature and demonstrates that the halogen-Ag bond is not very sensitive to the surface crystallography.     

Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

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.     

Laser-induced etching of titanium by Br2 and CCl3Br at 248 nm

A quartz crystal microbalance (QCM) has been used to study the KrF* excimer laser-induced etching of titanium by bromine-containing compounds. The experiment consists of focusing the pulsed UV laser beam at normal incidence onto the surface of a quartz crystal coated with 1 m of polycrystalline titanium. The removal of titanium from the surface is monitored in real time by measuring the change in the frequency of the quartz crystal. The dependence of the etch rate on etchant pressure and laser fluence was measured and found to be consistent with a two-step etching mechanism. The initial step in the etching of titanium is reaction between the etchant and the surface to form the etch product between laser pulses. The etch product is subsequently removed from the surface during the laser pulse via a laser-induced thermal desorption process. The maximum etch rate obtained in this work was 6.2 Å-pulse^–1, indicating that between two and three atomic layers of Ti can be removed per laser pulse. The energy required for desorption of the etch product is calculated to be 172 kJ-mole^–1, which is consistent with the sublimation enthalpy of TiBr₂ (168 kJ-mole^–1). The proposed product in the etching of titanium by Br₂ and CCl₃Br is thus TiBr₂. In the etching of Ti by Br₂, formation of TiBr₂ proceeds predominantly through the dissociative chemisorption of Br₂. In the case of etching with CCl₃Br, TiBr₂ is formed via chemisorption of Br atoms produced in the gas-phase photodissociation of CCl₃Br.     

Transition energies of ND4Cl and ND4Br in the transition I⇄II

The energy of the transition I?II of ND₄Cl and ND₄Br was measured by using a direct differential calorimetric method. The results 1024 cal/mole for ND₄Cl and 847 cal/mole for ND₄Br were obtained. The accuracy was estimated to be about 2%. The approximate transition temperatures 169°C for ND₄Cl and 118°C for ND₄Br were observed.